CN105190968A - Binder for use in electrochemical device electrodes, particle composite for use in electrochemical device electrodes, electrochemical device electrode, electrochemical device, and electrochemical device electrode manufacturing method - Google Patents
Binder for use in electrochemical device electrodes, particle composite for use in electrochemical device electrodes, electrochemical device electrode, electrochemical device, and electrochemical device electrode manufacturing method Download PDFInfo
- Publication number
- CN105190968A CN105190968A CN201480026238.XA CN201480026238A CN105190968A CN 105190968 A CN105190968 A CN 105190968A CN 201480026238 A CN201480026238 A CN 201480026238A CN 105190968 A CN105190968 A CN 105190968A
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- China
- Prior art keywords
- electrode
- binder
- electrochemical element
- particulate polymer
- electrodes
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- 239000011230 binding agent Substances 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 158
- 239000011164 primary particle Substances 0.000 claims abstract description 44
- 230000009477 glass transition Effects 0.000 claims abstract description 38
- 239000011246 composite particle Substances 0.000 claims abstract description 11
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- 239000007772 electrode material Substances 0.000 claims description 61
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明的目的在于提供由于在电极层形成时不制作浆料因此电极的生产性优异、由于作为分散剂不需要水溶性高分子成分因此能够实现低电阻化,且得到的电极的厚度精度及柔软性优异的电化学元件电极用粘合剂、使用了其的电极用复合体、电极、电化学元件以及电化学元件的制造方法。本发明涉及的电化学元件电极用粘合剂由玻璃化转变温度为35~80℃、初级粒子的体积基准D50平均粒径为80~1000nm的聚合物形成,其120℃的挥发成分少于1重量%,且该粘合剂为粉末状复合化粒子。The object of the present invention is to provide an electrode that is excellent in productivity because no slurry is prepared at the time of electrode layer formation, can achieve low resistance because a water-soluble polymer component is not required as a dispersant, and provides an electrode that has thickness accuracy and flexibility. A binder for an electrode of an electrochemical element having excellent properties, a composite for an electrode using the same, an electrode, an electrochemical element, and a method for producing an electrochemical element. The binder for electrochemical element electrodes related to the present invention is formed of a polymer with a glass transition temperature of 35 to 80°C and an average particle diameter of 80 to 1000 nm on a volume basis D50 of primary particles, and its volatile component at 120°C is less than 1 % by weight, and the binder is a powdery composite particle.
Description
技术领域technical field
本发明涉及电化学元件电极用粘合剂、电化学元件电极用粒子复合体、电化学元件电极、电化学元件及电化学元件电极的制造方法。The present invention relates to a binder for electrochemical element electrodes, a particle composite for electrochemical element electrodes, an electrochemical element electrode, an electrochemical element, and a method for producing an electrochemical element electrode.
背景技术Background technique
锂离子二次电池、双电层电容器以及锂离子电容器等电化学元件具有小型、轻质、能量密度高、并且能够反复充放电的特性,有效利用这样的特性,使得其需求迅速扩大。锂离子二次电池因为能量密度较大,因而已被用于手机、笔记本型个人电脑等移动领域。另一方面,双电层电容器因为能够迅速地充放电,因此已被用作个人电脑等的备用存储小型电源,另外,还期待双电层电容器作为电动汽车等的辅助电源的应用。进一步地,就有效利用了锂离子二次电池和双电层电容器的优点的锂离子电容器而言,由于其能量密度、输出密度均比双电层电容器高,因此已展开了将其适用于双电层电容器所适用的用途、以及以双电层电容器的性能而未能满足规格的用途的研究。这些之中,特别是对于锂离子二次电池,近年来,不仅对其在混合动力电动汽车、电动汽车等车载用途中的应用、甚至对于其在蓄电用途方面的应用均进行了探讨。Electrochemical components such as lithium-ion secondary batteries, electric double-layer capacitors, and lithium-ion capacitors are small, lightweight, have high energy density, and can be repeatedly charged and discharged. The effective use of these characteristics has rapidly expanded their demand. Lithium-ion secondary batteries have been used in the mobile field such as mobile phones and notebook personal computers because of their high energy density. On the other hand, electric double layer capacitors have been used as small power sources for backup storage of personal computers and the like because they can be rapidly charged and discharged. In addition, electric double layer capacitors are also expected to be used as auxiliary power sources for electric vehicles and the like. Furthermore, as for lithium ion capacitors that effectively utilize the advantages of lithium ion secondary batteries and electric double layer capacitors, since their energy density and output density are higher than those of electric double layer capacitors, they have been applied to double layer capacitors. Research on applications where electric layer capacitors are suitable and applications where the performance of electric double layer capacitors does not meet the specifications. Among them, lithium ion secondary batteries have been studied in recent years not only for their application to vehicle-mounted applications such as hybrid electric vehicles and electric vehicles, but also for their application to power storage applications.
在对这些电化学元件的期待升高的另一方面,对于这些电化学元件,伴随其用途的扩大及发展,对于低电阻化、高容量化、机械特性、生产性的提高等也要求进一步的改善。在这样的状况下,对于电化学元件用电极,也要求生产性更高的制造方法。On the other hand, expectations for these electrochemical elements are increasing, and further improvements in low resistance, high capacity, mechanical properties, and productivity are also required for these electrochemical elements along with the expansion and development of their applications. improve. Under such circumstances, a more productive manufacturing method is also required for electrodes for electrochemical elements.
电化学元件用电极通常是在集电体上叠层电极活性物质层而成的,所述电极活性物质层是通过将电极活性物质和根据需要而采用的导电剂利用粘合剂进行粘结而形成的。在电化学元件用电极中,有利用通过将含有电极活性物质、粘合剂、导电剂等的涂布电极用浆料涂布在集电体上并利用热等而除去溶剂的方法而制造的涂布电极。例如,在专利文献1中,记载了使用将聚合物挤出成膜状并进行粉碎而得到的聚合物粒子作为粘合剂,混合该粘合剂、电极活性物质、导电剂及溶剂得到涂布电极用浆料并涂布在集电体上从而得到涂布电极的方案。需要说明的是,在专利文献1中使用的聚合物粒子是经干燥的粘合剂、即干粘合剂。An electrode for an electrochemical element is usually formed by laminating an electrode active material layer on a current collector. The electrode active material layer is formed by bonding an electrode active material and an optionally used conductive agent with a binder Forming. Among the electrodes for electrochemical elements, there are those produced by applying a coating electrode slurry containing an electrode active material, a binder, a conductive agent, etc. on a current collector, and removing the solvent by using heat, etc. Coated electrodes. For example, in Patent Document 1, it is described that polymer particles extruded into a film form and pulverized are used as a binder, and the binder, electrode active material, conductive agent and solvent are mixed to obtain a coating. The electrode slurry is coated on the current collector to obtain a solution for coating the electrode. In addition, the polymer particle used in patent document 1 is a dried binder, ie, a dry binder.
但是,就这些方法而言,由于需要用于干燥聚合物膜、从涂布电极用浆料中除去溶剂的能量,因此存在导致成本升高、难以提高生产性的情况。However, these methods require energy for drying the polymer film and removing the solvent from the slurry for coating electrodes, which may lead to an increase in cost and make it difficult to improve productivity.
于是,提出了不使用涂布电极用浆料来制造电极的方法。例如,在专利文献2中,使用通过将干粘合剂或分散于溶剂中的粘合剂、电极活性物质、包含碳材料的导电剂混合并进行干燥而得到的粉末状混合物而形成了电极活性物质层。另外,在专利文献3中,使用将碳粉末和粘合剂通过湿式来混合、然后进行干燥/粉碎而得到的混合粉末在锂一次电池的负极表面形成了被膜。Then, the method of manufacturing an electrode without using the slurry for coating electrodes is proposed. For example, in Patent Document 2, an electrode active material is formed using a powdery mixture obtained by mixing a dry binder or a binder dispersed in a solvent, an electrode active material, a conductive agent including a carbon material, and drying. material layer. In addition, in Patent Document 3, a coating is formed on the negative electrode surface of a lithium primary battery using a mixed powder obtained by wet mixing carbon powder and a binder, followed by drying and pulverization.
另外,已提出了不仅不使用涂布电极用浆料、而且不将粘合剂分散在溶剂中而得到电极材料而形成电极活性物质层的方法。例如,在专利文献4中,使用混合粉体而形成了电极活性物质层,该混合粉体是将电极活性物质、和利用在导电剂的存在下进行的悬浮聚合法而与导电剂发生了复合的粘合剂粒子进行混合而得到的。In addition, a method of forming an electrode active material layer by obtaining an electrode material without using not only the slurry for coating an electrode but also without dispersing a binder in a solvent has been proposed. For example, in Patent Document 4, an electrode active material layer is formed using a mixed powder in which an electrode active material is compounded with a conductive agent by a suspension polymerization method performed in the presence of a conductive agent. obtained by mixing binder particles.
另外,在专利文献5中,使用作为干粘合剂的聚偏氟乙烯(PVDF)粉末作为粘合剂,通过静电涂敷使将电极活性物质、粘合剂及导电剂混合而得到的混合粉末附着于集电体表面,然后,在粘合剂的软化点以上的温度使这些成分熔粘,由此在集电体上形成了电极活性物质层。In addition, in Patent Document 5, polyvinylidene fluoride (PVDF) powder as a dry binder is used as a binder, and a mixed powder obtained by mixing an electrode active material, a binder, and a conductive agent is electrostatically applied. After adhering to the surface of the current collector, these components are melted at a temperature equal to or higher than the softening point of the binder, whereby an electrode active material layer is formed on the current collector.
现有技术文献prior art literature
专利文献patent documents
专利文献1:国际公开第2007/122947号Patent Document 1: International Publication No. 2007/122947
专利文献2:日本专利4687458号公报Patent Document 2: Japanese Patent No. 4687458
专利文献3:日本特开2010-86738号公报Patent Document 3: Japanese Patent Laid-Open No. 2010-86738
专利文献4:日本特开2011-14409号公报Patent Document 4: Japanese Patent Laid-Open No. 2011-14409
专利文献5:日本特开2001-351616号公报Patent Document 5: Japanese Patent Laid-Open No. 2001-351616
发明内容Contents of the invention
发明要解决的问题The problem to be solved by the invention
然而,在将干粘合剂用作粘合剂、并使用通过干式将干粘合剂和电极活性物质混合而得到的电极材料来形成电极活性物质层的情况下,如果使用专利文献1中记载的粘合剂,则会因粘合剂的玻璃化转变温度过高而导致无法获得具有充分柔软性的电极。另外,如果使用专利文献2或5中记载的粘合剂,则由于粘合剂的玻璃化转变温度过低而难以形成均一的电极活性物质层。另外,在专利文献3和4中未记载使用干粘合剂。However, in the case of using a dry binder as a binder and using an electrode material obtained by dry mixing a dry binder and an electrode active material to form an electrode active material layer, if using the In the case of the binder described above, an electrode having sufficient flexibility cannot be obtained because the glass transition temperature of the binder is too high. In addition, if the binder described in Patent Document 2 or 5 is used, it is difficult to form a uniform electrode active material layer because the glass transition temperature of the binder is too low. In addition, Patent Documents 3 and 4 do not describe the use of a dry adhesive.
另外,如果使用专利文献5中使用的粘合剂,则由于粘合剂的粒径大,因此连接电极活性物质间的粘结点少,难以得到具有充分强度的电极。In addition, if the binder used in Patent Document 5 is used, since the particle size of the binder is large, there are few bonding points connecting electrode active materials, and it is difficult to obtain an electrode with sufficient strength.
本发明的目的在于提供由于在形成电极层时不制作浆料因此电极的生产性优异、由于作为分散剂不需要水溶性高分子成分因此能够实现低电阻化、并且所得电极的厚度精度及柔软性优异的电化学元件电极用粘合剂、使用了该电化学元件电极用粘合剂的电化学元件电极用粒子复合体、使用了该电化学元件电极用粒子复合体的电化学元件电极及电化学元件。进一步,本发明的目的在于提供生产性优异、厚度精度及柔软性优异的电化学元件电极的制造方法。The object of the present invention is to provide an electrode that is excellent in productivity because no slurry is prepared when forming an electrode layer, can achieve low resistance because a water-soluble polymer component is not required as a dispersant, and provides thickness accuracy and flexibility of the obtained electrode. Excellent binder for electrochemical element electrodes, particle composite for electrochemical element electrodes using the binder for electrochemical element electrodes, electrochemical element electrodes and electrodes for electrochemical element electrodes using the particle composite for electrochemical element electrodes chemical element. A further object of the present invention is to provide a method for producing an electrode for an electrochemical device that is excellent in productivity, thickness accuracy, and flexibility.
解决问题的方法way of solving the problem
本发明人为了解决上述问题而进行了深入研究,结果发现,通过将玻璃化转变温度及平均粒径控制在给定的范围,可以达成上述目的,从而完成了本发明。As a result of intensive studies to solve the above problems, the present inventors found that the above object can be achieved by controlling the glass transition temperature and the average particle diameter within a given range, and completed the present invention.
即,根据本发明,可提供:That is, according to the present invention, it is possible to provide:
(1)一种电化学元件电极用粘合剂,其由玻璃化转变温度为35~80℃、初级粒子的体积基准D50平均粒径为80~1000nm的聚合物形成,该粘合剂在120℃时的挥发成分少于1重量%,且该粘合剂为粉末状复合化粒子;(1) A binder for an electrode of an electrochemical element, which is formed by a polymer having a glass transition temperature of 35 to 80° C. and a volume basis D50 of primary particles having an average particle diameter of 80 to 1000 nm. The volatile component at °C is less than 1% by weight, and the binder is a powdery composite particle;
(2)根据(1)所述的电化学元件电极用粘合剂,其是通过将分散有所述聚合物的粒子状聚合物的水分散体在低于所述粒子状聚合物的最低制膜温度的条件下进行干燥而得到的;(2) The binder for electrochemical element electrodes according to (1), which is obtained by making an aqueous dispersion of a particulate polymer in which the polymer is dispersed at a temperature lower than the minimum concentration of the particulate polymer. Obtained by drying under the condition of film temperature;
(3)根据(1)或(2)所述的电化学元件电极用粘合剂,其包含选自下组中的至少一种单体单元:共轭二烯单体单元、丙烯酸酯单体单元、甲基丙烯酸酯单体单元、芳香族乙烯基化合物单体单元、烯属不饱和腈单体单元、烯属不饱和羧酸单体单元、烯属不饱和酰胺单体单元、多官能烯属单体单元;(3) The binder for electrochemical element electrodes according to (1) or (2), comprising at least one monomer unit selected from the group consisting of conjugated diene monomer units, acrylate monomers Unit, methacrylate monomer unit, aromatic vinyl compound monomer unit, ethylenically unsaturated nitrile monomer unit, ethylenically unsaturated carboxylic acid monomer unit, ethylenically unsaturated amide monomer unit, polyfunctional ethylenic is a single unit;
(4)一种电化学元件电极用粒子复合体,其是通过将电极活性物质和(1)~(3)中任一项所述的电化学元件电极用粘合剂进行干式混合而得到的;(4) A particle composite for electrochemical element electrodes obtained by dry mixing an electrode active material and the binder for electrochemical element electrodes according to any one of (1) to (3) of;
(5)根据(4)所述的电化学元件电极用粒子复合体,其中,该电化学元件电极用粒子复合体的体积基准D50平均粒径(Da)和所述电极活性物质的体积基准D50平均粒径(Db)之比(Da/Db)为0.5~2;(5) The particle composite for electrochemical element electrodes according to (4), wherein the particle composite for electrochemical element electrodes has an average particle diameter (Da) based on volume D50 and a volume basis D50 of the electrode active material. The average particle size (Db) ratio (Da/Db) is 0.5 to 2;
(6)一种电化学元件电极,其是在集电体上叠层包含(5)所述的电化学元件电极用粒子复合体的电极活性物质层而成的;(6) An electrochemical element electrode, which is formed by laminating an electrode active material layer comprising the particle composite for electrochemical element electrode described in (5) on a current collector;
(7)根据(6)所述的电化学元件电极,其中,所述电极活性物质层是通过将包含所述电化学元件电极用粒子复合体的电极材料在所述集电体上进行加压成型而得到的;(7) The electrochemical element electrode according to (6), wherein the electrode active material layer is formed by pressing an electrode material including the particle composite for electrochemical element electrode on the current collector. obtained by forming;
(8)一种电化学元件,其具备(6)或(7)所述的电化学元件电极;(8) An electrochemical element comprising the electrochemical element electrode described in (6) or (7);
(9)一种电化学元件电极的制造方法,其包括:将分散有玻璃化转变温度为35~80℃、初级粒子的体积基准平均粒径D50为80~1000nm的球形的粒子状聚合物的水分散体在低于所述粒子状聚合物的最低制膜温度的条件下进行干燥而得到粉末状复合化粒子的干燥工序;将所述粉末状复合化粒子和电极活性物质进行干式混合而得到粒子复合体的混合工序;以及使用所述粒子复合体来制造电极的电极制造工序。(9) A method for manufacturing an electrode of an electrochemical element, comprising: dispersing a spherical particulate polymer having a glass transition temperature of 35 to 80° C. and a volume-based average particle diameter D50 of primary particles of 80 to 1000 nm. A drying step in which the aqueous dispersion is dried at a temperature lower than the minimum film-forming temperature of the particulate polymer to obtain powdery composite particles; the powdery composite particles and electrode active materials are dry-mixed to form a mixing step of obtaining a particle composite; and an electrode manufacturing step of using the particle composite to manufacture an electrode.
发明的效果The effect of the invention
根据本发明,可提供由于形成电极层时不制作浆料因此电极的生产性优异、由于作为分散剂不需要水溶性高分子因此能够实现低电阻化、并且所得电极的厚度精度及柔软性优异的电化学元件电极用粘合剂、使用了该电化学元件电极用粘合剂的电化学元件电极用粒子复合体、使用了该电化学元件电极用粒子复合体的电化学元件电极及电化学元件。进一步,根据本发明,可提供生产性优异、厚度精度及柔软性优异的电化学元件电极的制造方法。According to the present invention, it is possible to provide an electrode that is excellent in productivity because no slurry is prepared when forming an electrode layer, can achieve low resistance because a water-soluble polymer is not required as a dispersant, and has excellent thickness accuracy and flexibility of the resulting electrode. Binder for electrochemical element electrodes, particle composite for electrochemical element electrodes using the binder for electrochemical element electrodes, electrochemical element electrode and electrochemical element using the particle composite for electrochemical element electrodes . Furthermore, according to the present invention, it is possible to provide a method for manufacturing an electrode of an electrochemical device that is excellent in productivity, thickness accuracy, and flexibility.
具体实施方式Detailed ways
以下,针对本发明的电化学元件电极用粘合剂进行说明。本发明的电化学元件电极用粘合剂(以下也记作“电极用粘合剂”)的特征在于,其包含玻璃化转变温度为35~80℃、初级粒子的体积基准D50平均粒径为80~1000nm的聚合物,且该粘合剂在120℃时的挥发成分少于1重量%,该粘合剂为粉末状复合化粒子。Hereinafter, the binder for electrochemical element electrodes of this invention is demonstrated. The binder for electrochemical element electrodes of the present invention (hereinafter also referred to as "binder for electrodes") is characterized in that it has a glass transition temperature of 35 to 80° C., and a volume basis D50 average particle diameter of the primary particles of 80-1000nm polymer, and the volatile component of the binder is less than 1% by weight at 120°C, and the binder is a powdery composite particle.
需要说明的是,在本说明书中,所述“正极活性物质”是指正极用的电极活性物质,所述“负极活性物质”是指负极用的电极活性物质。此外,所述“正极活性物质层”是指设置于正极的电极活性物质层,所述“负极活性物质层”是指设置于负极的电极活性物质层。It should be noted that, in this specification, the "positive electrode active material" refers to an electrode active material for a positive electrode, and the "negative electrode active material" refers to an electrode active material for a negative electrode. In addition, the "positive electrode active material layer" refers to the electrode active material layer provided on the positive electrode, and the "negative electrode active material layer" refers to the electrode active material layer provided on the negative electrode.
(电化学元件电极用粘合剂)(Binder for electrodes of electrochemical devices)
本发明的电极用粘合剂的玻璃化转变温度(Tg)为35~80℃、优选为40~75℃、更优选为40~70℃、进一步优选为40~60℃、特别优选为45~55℃。如果电极用粘合剂的玻璃化转变温度在该范围,则可获得柔软且充分强度的电极。另外,如果电极用粘合剂的玻璃化转变温度过高,则会变得难以获得具有充分的柔软性的电极。另外,如果电极用粘合剂的玻璃化转变温度过低,则由于后述的粒子复合体的流动性不充分,因此会导致所得电极的厚度精度变差。即,会导致电极会发生厚度不均。The glass transition temperature (Tg) of the electrode binder of the present invention is 35 to 80°C, preferably 40 to 75°C, more preferably 40 to 70°C, even more preferably 40 to 60°C, particularly preferably 45 to 70°C. 55°C. When the glass transition temperature of the binder for electrodes is within this range, a flexible electrode having sufficient strength can be obtained. Moreover, when the glass transition temperature of the binder for electrodes is too high, it will become difficult to obtain the electrode which has sufficient flexibility. In addition, if the glass transition temperature of the binder for electrodes is too low, the fluidity of the particle composite described later will be insufficient, and thus the thickness accuracy of the obtained electrode will deteriorate. That is, thickness unevenness of the electrodes may occur.
本发明的电极用粘合剂的初级粒子的体积基准D50平均粒径(以下也称为“初级粒径”)为80~1000nm、优选为80~800nm、更优选为100~500nm、进一步优选为130~400nm。如果电极用粘合剂的初级粒径在该范围,则可以充分地保持集电体和电极活性物质之间的粘接强度。另外,如果电极用粘合剂的初级粒径过大,则由于粘接性降低,因此在进行后述的电极的柔软性试验时会发生掉粉。另外,如果电极用粘合剂的初级粒径过小,则会因电极用粘合剂难以分散而导致粘接性降低。The volume-based D50 average particle diameter (hereinafter also referred to as "primary particle diameter") of the primary particles of the electrode binder of the present invention is 80 to 1000 nm, preferably 80 to 800 nm, more preferably 100 to 500 nm, and even more preferably 130~400nm. When the primary particle diameter of the electrode binder is within this range, the adhesive strength between the current collector and the electrode active material can be maintained sufficiently. Moreover, when the primary particle diameter of the binder for electrodes is too large, since adhesiveness will fall, powder fall-off will generate|occur|produce in the flexibility test of an electrode mentioned later. Moreover, when the primary particle diameter of the binder for electrodes is too small, it will become difficult to disperse|distribute the binder for electrodes, and adhesiveness will fall.
需要说明的是,通过将利用如下所述的聚合方法得到的粒子状聚合物的水分散体进行干燥可得到电极用粘合剂,但该水分散体中的粒子状聚合物的初级粒径为上述范围。另外,粒子状聚合物的形状优选为球形。It should be noted that the binder for electrodes can be obtained by drying the aqueous dispersion of the particulate polymer obtained by the polymerization method described below, but the primary particle diameter of the particulate polymer in the aqueous dispersion is the above range. In addition, the shape of the particulate polymer is preferably spherical.
粒子状聚合物为球形是指,在将短轴直径设为Ls、长轴直径设为Ll、并使La=(Ls+Ll)/2、将(1-(Ll-Ls)/La)×100的值设为球形度(%)时,球形度为80%以上。The particulate polymer is spherical means that when the short-axis diameter is Ls, the long-axis diameter is L1, and La=(Ls+L1)/2, (1-(L1-Ls)/La)× When the value of 100 is defined as the sphericity (%), the sphericity is 80% or more.
这里,短轴直径Ls和长轴直径Ll是通过观察透射型或扫描型电子显微镜的照片而测定的例如10~30个等给定数量的聚合物粒子的长轴直径(Ll)及短轴直径(Ls)各自的平均值。另外,La是可通过计算La=(Ls+Ll)/2而求出的值。Here, the short-axis diameter Ls and the long-axis diameter L1 are the long-axis diameter (L1) and the short-axis diameter of a given number of polymer particles, such as 10 to 30, measured by observing photographs of a transmission or scanning electron microscope. (Ls) respective mean values. In addition, La is a value obtained by calculating La=(Ls+Ll)/2.
此外,本发明的电极用粘合剂在120℃时的挥发成分少于1重量%。如果电极用粘合剂在120℃时的挥发成分在该范围,则电极用粘合剂可均一地分散、得到具有充分强度的电极。另外,由于后述的粒子复合体的流动性也变得良好,因此可以得到厚度精度良好的电极。另外,如果电极用粘合剂在120℃时的挥发成分过多,则由于在制造粒子复合体时电极用粘合剂不分散,因此无法获得具有充分强度的电极,另外,由于粒子复合体的流动性不充分,因此得到的电极的厚度精度变差。In addition, the binder for electrodes of the present invention has a volatile component of less than 1% by weight at 120°C. When the volatile component of the electrode binder at 120° C. is within this range, the electrode binder can be uniformly dispersed and an electrode having sufficient strength can be obtained. In addition, since the fluidity of the particle composite to be described later is also improved, an electrode with excellent thickness accuracy can be obtained. In addition, if the volatile component of the binder for electrodes is too much at 120°C, the binder for electrodes will not be dispersed when the particle composite is produced, so an electrode with sufficient strength cannot be obtained. Since fluidity is insufficient, the thickness precision of the obtained electrode deteriorates.
另外,本发明的电极用粘合剂以球形或多个球结合而成的形状(球的凝聚体)的粉末状即粉末状复合化粒子的形式存在。上述电极用粘合剂的初级粒子也可以以各自独立的粒子形式存在,但通常是由多个初级粒子在保持其形状的情况下通过分子间力等结合而形成一个粒子。此外,就由多个初级粒子形成的粒子而言,有时会因外力作用而导致初级粒子以各自独立的粒子的形式存在。通过使电极用粘合剂的形状为球形或多个球结合而成的形状,可以确保粒子复合体的流动性。In addition, the binder for electrodes of the present invention exists in the form of powdery, ie, powdery composite particles having a spherical shape or a shape in which a plurality of spheres are bonded (aggregate of spheres). The primary particles of the above-mentioned electrode binder may exist as independent particles, but usually a plurality of primary particles are bonded by intermolecular force while maintaining their shape to form one particle. In addition, in the case of particles composed of a plurality of primary particles, the primary particles may exist as independent particles due to an external force. The fluidity of the particle composite can be ensured by making the shape of the electrode binder into a spherical shape or a shape in which a plurality of balls are bonded.
本发明的电极用粘合剂优选包含选自共轭二烯单体单元、(甲基)丙烯酸酯单体单元、芳香族乙烯基化合物单体单元、烯属不饱和腈单体单元、烯属不饱和羧酸单体单元、烯属不饱和酰胺单体单元、多官能烯属单体单元中的至少一种单体单元。需要说明的是,在本说明书中,所述“(甲基)丙烯酸”表示“丙烯酸”和“甲基丙烯酸”。The electrode binder of the present invention preferably comprises a monomer unit selected from a conjugated diene monomer unit, a (meth)acrylate monomer unit, an aromatic vinyl compound monomer unit, an ethylenically unsaturated nitrile monomer unit, an ethylenically unsaturated nitrile monomer unit, an ethylenically unsaturated nitrile monomer unit, At least one monomer unit of an unsaturated carboxylic acid monomer unit, an ethylenically unsaturated amide monomer unit, and a polyfunctional ethylenic monomer unit. In addition, in this specification, the said "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid."
作为形成共轭二烯单体单元的共轭二烯单体,可列举:1,3-丁二烯、异戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯等碳原子数为4以上的共轭二烯。在这些中,优选1,3-丁二烯。Examples of the conjugated diene monomer forming the conjugated diene monomer unit include: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1 , Conjugated dienes having 4 or more carbon atoms such as 3-pentadiene. Among these, 1,3-butadiene is preferred.
作为形成(甲基)丙烯酸酯单体单元的(甲基)丙烯酸酯单体,可列举:丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸2-乙基己酯、丙烯酸壬酯、丙烯酸癸酯、丙烯酸月桂酯、丙烯酸正十四烷基酯、丙烯酸硬脂酯等丙烯酸烷基酯;甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸戊酯、甲基丙烯酸己酯、甲基丙烯酸庚酯、甲基丙烯酸辛酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸壬酯、甲基丙烯酸癸酯、甲基丙烯酸月桂酯、甲基丙烯酸正十四烷基酯、甲基丙烯酸硬脂酯等甲基丙烯酸烷基酯等。其中,由于可提高电极的柔软性,在制作卷绕电池时可抑制电极的剥离,且使用了该电极的二次电池的特性(循环特性等)优异,因此优选与非羰基性氧原子结合的烷基的碳原子数为4以上的丙烯酸烷基酯或甲基丙烯酸烷基酯,更优选与非羰基性氧原子结合的烷基的碳原子数为6以上且20以下的丙烯酸烷基酯或甲基丙烯酸烷基酯。Examples of (meth)acrylate monomers that form (meth)acrylate monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and tert-butyl acrylate. ester, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate and other alkyl acrylates; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate ester, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, methyl Alkyl methacrylates such as n-tetradecyl acrylate and stearyl methacrylate, etc. Among them, since the flexibility of the electrode can be improved, the peeling of the electrode can be suppressed when the wound battery is produced, and the characteristics (cycle characteristics, etc.) of the secondary battery using the electrode are excellent, so those bonded to non-carbonyl oxygen atoms are preferred. An alkyl acrylate or methacrylate having an alkyl group having 4 or more carbon atoms, more preferably an alkyl acrylate or methacrylate having an alkyl group having 6 or more and 20 or less carbon atoms bonded to a non-carbonyl oxygen atom. Alkyl methacrylate.
作为形成芳香族乙烯基化合物单体单元的芳香族乙烯基化合物单体,可列举:苯乙烯、α-甲基苯乙烯、乙烯基甲苯等。Examples of the aromatic vinyl compound monomer forming the aromatic vinyl compound monomer unit include styrene, α-methylstyrene, vinyltoluene, and the like.
作为形成α,β-烯属不饱和腈单体单元的单体,只要是具有腈基的α,β-烯属不饱和化合物则没有限定,可列举:丙烯腈;α-氯丙烯腈、α-溴丙烯腈等α-卤代丙烯腈;甲基丙烯腈等α-烷基丙烯腈;等等,优选丙烯腈和甲基丙烯腈。作为α,β-烯属不饱和腈单体,也可以将这些中的多种组合使用。The monomer forming the α,β-ethylenically unsaturated nitrile monomer unit is not limited as long as it is an α,β-ethylenically unsaturated compound having a nitrile group, and examples thereof include: acrylonitrile; α-chloroacrylonitrile, α - α-haloacrylonitrile such as bromoacrylonitrile; α-alkylacrylonitrile such as methacrylonitrile; etc., preferably acrylonitrile and methacrylonitrile. As the α,β-ethylenically unsaturated nitrile monomer, these may be used in combination of multiple types.
作为形成烯属不饱和羧酸单体单元的烯属不饱和羧酸单体,可列举:丙烯酸、甲基丙烯酸、马来酸、富马酸、衣康酸等。Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. are mentioned as an ethylenic unsaturated carboxylic acid monomer which forms an ethylenic unsaturated carboxylic monomer unit.
作为形成烯属不饱和酰胺单体单元的烯属不饱和酰胺单体,可列举:(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N,N'-二羟甲基(甲基)丙烯酰胺等。Examples of the ethylenically unsaturated amide monomer forming the ethylenically unsaturated amide monomer unit include: (meth)acrylamide, N-methylol (meth)acrylamide, N,N'-dimethylol (meth)acrylamide, etc.
作为形成多官能烯属不饱和单体单元的具有2个以上烯烃性双键的多官能烯属不饱和单体,可列举:二乙烯基苯等二乙烯基化合物;乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯类;三羟甲基丙烷三(甲基)丙烯酸酯等三甲基丙烯酸酯类;等等。Examples of polyfunctional ethylenically unsaturated monomers having two or more olefinic double bonds that form polyfunctional ethylenically unsaturated monomer units include: divinyl compounds such as divinylbenzene; ethylene glycol di(methyl ) acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate and other di(meth)acrylates; trimethylolpropane tri(meth)acrylate and other three Methacrylates; etc.
对于使各单体聚合的方法没有特别地制限,但例如优选使用如下方法:使用十二烷基苯磺酸钠等乳化剂得到粒子状聚合物的胶乳(水分散体)的乳液聚合法、使用聚乙烯醇等分散剂得到粒子状聚合物的水分散体的悬浮聚合法(也包括微悬浮聚合法)等。在这些方法中,由于聚合反应控制容易,因此更优选乳液聚合法。There are no particular limitations on the method of polymerizing each monomer, but for example, the following methods are preferably used: an emulsion polymerization method using an emulsifier such as sodium dodecylbenzenesulfonate to obtain a latex (aqueous dispersion) of a particulate polymer, using Dispersants such as polyvinyl alcohol can be used to obtain a suspension polymerization method (including a microsuspension polymerization method) of an aqueous dispersion of a particulate polymer. Among these methods, the emulsion polymerization method is more preferable because the control of the polymerization reaction is easy.
另外,本发明的电极用粘合剂可以通过使由各单体聚合而得到的聚合物干燥而获得。即,通过使聚合物干燥,可以获得作为粉末状的复合化粒子的电极用粘合剂(粉末状粘合剂)。就干燥方法而言,只要不会使粒子状聚合物的初级粒子彼此间过度地粘接、能够以再分散的状态进行干燥即可,没有特别地限制,但可列举例如:使粒子状聚合物的水分散体喷雾干燥的方法、利用旋转蒸发仪进行干燥的方法等。另外,更优选利用喷雾干燥、旋转蒸发仪进行干燥后,在真空条件下进行干燥。Moreover, the binder for electrodes of this invention can be obtained by drying the polymer obtained by polymerizing each monomer. That is, by drying the polymer, a binder for electrodes (powder binder) can be obtained as powdery composite particles. The drying method is not particularly limited as long as the primary particles of the particulate polymer are not excessively bonded to each other and can be dried in a redispersed state, but examples include: drying the particulate polymer The method of spray-drying the aqueous dispersion, the method of using a rotary evaporator to dry, etc. In addition, it is more preferable to dry under vacuum conditions after drying by spray drying or a rotary evaporator.
作为干燥温度,从不会导致粒子状聚合物的初级粒子彼此间过度地粘接、能够以再分散的状态除去水分的观点出发,优选低于粒子状聚合物的最低制膜温度的温度。如果干燥温度过高,则由于会导致粒子状聚合物发生膜化而难以进行再分散。The drying temperature is preferably a temperature lower than the minimum film-forming temperature of the particulate polymer from the viewpoint of being able to remove water in a redispersed state without causing excessive adhesion of primary particles of the particulate polymer. If the drying temperature is too high, redispersion will be difficult because the particulate polymer will be filmed.
另外,从能够以再分散的状态使粒子状聚合物干燥、能够兼顾后述的粒子复合体的流动性及电极形成后的电极的柔软性的观点出发,粒子状聚合物的最低制膜温度优选为35~100℃。如果粒子状聚合物的最低制膜温度过高,则会导致所得电极的柔软性下降。另外,如果粒子状聚合物的最低制膜温度过低,则难以在不导致粒子状聚合物的初级粒子过度粘接的情况下使其干燥。即,难以使粒子状聚合物以能够再分散的状态干燥。In addition, the minimum film-forming temperature of the particulate polymer is preferably It is 35-100°C. When the minimum film-forming temperature of a particulate-form polymer is too high, the flexibility of the electrode obtained will fall. In addition, if the minimum film-forming temperature of the particulate polymer is too low, it will be difficult to dry the particulate polymer without causing excessive adhesion of primary particles of the particulate polymer. That is, it is difficult to dry the particulate polymer in a redispersible state.
在此,最低制膜温度是可形成上述粒子状聚合物的膜的最低温度。最低制膜温度例如可以基于JISK6828-2(2003)、ISO2115进行测定。具体来说,在具有适当温度梯度的铁板等平板上涂布粒子状聚合物的水分散液并进行干燥、使其达到约100μm的厚度,并测定发生了膜化的部分和未发生膜化的部分之间的临界温度。这里,由于发生了膜化的部分变得透明,而未发生膜化的部分呈白浊,因此可以通过目测而确认发生了膜化的部分和未发生膜化的部分的交界。另外,由于在对涂布粒子状聚合物的水分散体并干燥后的平板进行擦蹭的情况下,未发生膜化的部分会发生掉粉,因此,也可以根据掉粉的有无来确认发生了膜化的部分和未发生膜化的部分的交界。Here, the lowest film forming temperature is the lowest temperature at which a film of the aforementioned particulate polymer can be formed. The minimum film formation temperature can be measured based on JISK6828-2 (2003) and ISO2115, for example. Specifically, on a flat plate such as an iron plate with an appropriate temperature gradient, the aqueous dispersion of the particulate polymer is coated and dried to a thickness of about 100 μm, and the filmed and non-filmed parts are measured. The critical temperature between the parts. Here, since the filmed part became transparent and the non-filmed part became cloudy, the boundary between the filmed part and the non-filmed part could be confirmed visually. In addition, when rubbing the flat plate after applying the aqueous dispersion of the particulate polymer and drying it, powder falling off occurs in the part where the film does not occur, so it can also be confirmed by the presence or absence of powder falling. The boundary between the filmed part and the non-filmed part.
(电化学元件电极用粒子复合体)(Particle composites for electrodes of electrochemical devices)
本发明的电化学元件电极用粒子复合体(以下也称为“粒子复合体”)包含上述电极用粘合剂和电极活性物质。粒子复合体也可以根据需要而包含导电剂。这里,在粒子复合体中,电极用粘合剂和电极活性物质也可以分别以各自独立的粒子的形式存在,但通常是在电极活性物质的表面附着多个电极用粘合剂而形成一个粒子。进而,电极用粘合剂和电极活性物质的各自独立粒子、及上述的一个粒子,以实质上保持形状的状态由多个结合而形成二次粒子。另外,就该二次粒子而言,在受到外力的情况下,其初级粒子有时会以各自独立的粒子的形式存在。The particle composite for electrochemical device electrodes (hereinafter also referred to as "particle composite") of the present invention includes the above-mentioned binder for electrodes and an electrode active material. The particle composite may contain a conductive agent as needed. Here, in the particle composite, the electrode binder and the electrode active material may also exist in the form of independent particles, but usually a plurality of electrode binders are attached to the surface of the electrode active material to form one particle. . Furthermore, the independent particles of the electrode binder and the electrode active material, and the above-mentioned one particle are combined in a plurality in a state where the shape is substantially maintained to form secondary particles. In addition, when external force is applied to the secondary particles, the primary particles may exist as independent particles.
(电极活性物质)(electrode active material)
作为本发明的电化学元件为锂离子二次电池的情况下的正极活性物质,可使用能够掺杂及脱掺杂锂离子的活性物质,其大致分为由无机化合物构成的活性物质和由有机化合物构成的活性物质。As the positive electrode active material in the case where the electrochemical element of the present invention is a lithium ion secondary battery, an active material capable of doping and dedoping lithium ions can be used, which can be roughly divided into active materials composed of inorganic compounds and active materials composed of organic compounds. Active substances composed of compounds.
作为由无机化合物构成的正极活性物质,可以举出:过渡金属氧化物、过渡金属硫化物、锂和过渡金属形成的含锂复合金属氧化物等。作为上述过渡金属,可以使用Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Mo等。Examples of the positive electrode active material composed of inorganic compounds include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides formed of lithium and transition metals, and the like. As the above-mentioned transition metal, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, etc. can be used.
作为过渡金属氧化物,可以列举:MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3、非晶质V2O-P2O5、MoO3、V2O5、V6O13等,其中,从循环稳定性和容量的观点出发,优选MnO、V2O5、V6O13、TiO2。作为过渡金属硫化物,可以举出:TiS2、TiS3、非晶质MoS2、FeS等。作为含锂复合金属氧化物,可以列举:具有层状结构的含锂复合金属氧化物、具有尖晶石结构的含锂复合金属氧化物、具有橄榄石型结构的含锂复合金属氧化物等。Examples of transition metal oxides include: MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 OP 2 O 5 , MoO 3 , V 2 O 5. V 6 O 13 , etc. Among them, MnO, V 2 O 5 , V 6 O 13 , and TiO 2 are preferable from the viewpoint of cycle stability and capacity. Examples of transition metal sulfides include TiS 2 , TiS 3 , amorphous MoS 2 , FeS, and the like. Examples of lithium-containing composite metal oxides include lithium-containing composite metal oxides having a layered structure, lithium-containing composite metal oxides having a spinel structure, lithium-containing composite metal oxides having an olivine structure, and the like.
作为具有层状结构的含锂复合金属氧化物,可以举出:含锂的钴氧化物(LiCoO2)、含锂的镍氧化物(LiNiO2)、Co-Ni-Mn的锂复合氧化物、Ni-Mn-Al的锂复合氧化物、Ni-Co-Al的锂复合氧化物等。作为具有尖晶石结构的含锂复合金属氧化物,可以举出:锰酸锂(LiMn2O4)、将Mn的一部分用其他过渡金属置换而成的Li[Mn3/2M1/2]O4(在此,M为Cr、Fe、Co、Ni、Cu等)等。作为具有橄榄石型结构的含锂复合金属氧化物,可以举出:LixMPO4(式中,M表示选自Mn、Fe、Co、Ni、Cu、Mg、Zn、V、Ca、Sr、Ba、Ti、Al、Si、B及Mo中的至少1种,0≤X≤2)所示的橄榄石型磷酸锂化合物。Examples of lithium-containing composite metal oxides having a layered structure include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), lithium composite oxide of Co-Ni-Mn, Ni-Mn-Al lithium composite oxide, Ni-Co-Al lithium composite oxide, and the like. Examples of lithium-containing composite metal oxides having a spinel structure include lithium manganate (LiMn 2 O 4 ), and Li[Mn 3/2 M 1/2 ] obtained by substituting a part of Mn with other transition metals. ]O 4 (here, M is Cr, Fe, Co, Ni, Cu, etc.) and the like. Lithium-containing composite metal oxides having an olivine-type structure include: Li x MPO 4 (wherein, M is selected from the group consisting of Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, An olivine-type lithium phosphate compound represented by at least one of Ba, Ti, Al, Si, B, and Mo, 0≤X≤2).
作为有机化合物,也可以使用例如聚乙炔、聚对苯等导电性高分子。对于导电性不足的铁系氧化物,可以通过在进行还原烧制时使碳源物质存在,从而将其制成由碳材料覆盖的正极活性物质使用。此外,也可以使用对这些化合物进行部分元素置换而成的物质。正极活性物质也可以为上述的无机化合物和有机化合物的混合物。As the organic compound, for example, conductive polymers such as polyacetylene and polyparaphenylene can also be used. Iron-based oxides having insufficient electrical conductivity can be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to exist during reduction firing. In addition, those obtained by substituting some elements of these compounds can also be used. The positive electrode active material may also be a mixture of the above-mentioned inorganic compounds and organic compounds.
作为电化学元件为锂离子电容器的情况下的正极活性物质,只要是能够可逆地负载锂离子和例如四氟硼酸盐这样的阴离子的物质即可。具体而言,可优选使用碳的同素异形体,可广泛使用在双电层电容器中被使用的电极活性物质。作为碳的同素异形体的具体例,可以列举:活性炭、多并苯(PAS)、碳晶须、碳纳米管及石墨等。The positive electrode active material in the case where the electrochemical element is a lithium ion capacitor may be any material that can reversibly support lithium ions and anions such as tetrafluoroborate. Specifically, carbon allotropes can be preferably used, and electrode active materials used in electric double layer capacitors can be widely used. Specific examples of carbon allotropes include activated carbon, polyacene (PAS), carbon whiskers, carbon nanotubes, and graphite.
作为本发明的电化学元件为锂离子二次电池的情况下的负极活性物质,例如可以列举:无定形碳、石墨、天然石墨、中间相碳微球、沥青类碳纤维等碳质材料;多并苯等导电性高分子;硅、锡、锌、锰、铁、镍等金属或它们的合金;上述金属或合金的氧化物或硫酸盐;金属锂;Li-Al、Li-Bi-Cd、Li-Sn-Cd等锂合金;锂过渡金属氮化物;硅等。另外,作为负极活性物质,也可以使用在该负极活性物质的粒子的表面通过例如机械改性法附着了导电剂而成的物质。另外,负极活性物质可以单独使用1种,也可以以任意比率组合使用2种以上。As the negative electrode active material under the situation of lithium ion secondary battery as the electrochemical element of the present invention, for example can enumerate: Carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microsphere, pitch carbon fiber; Conductive polymers such as benzene; metals such as silicon, tin, zinc, manganese, iron, nickel or their alloys; oxides or sulfates of the above metals or alloys; lithium metal; Li-Al, Li-Bi-Cd, Li -Sn-Cd and other lithium alloys; lithium transition metal nitrides; silicon, etc. In addition, as the negative electrode active material, what is obtained by adhering a conductive agent to the surface of the particles of the negative electrode active material by, for example, a mechanical modification method can also be used. In addition, one type of negative electrode active material may be used alone, or two or more types may be used in combination at an arbitrary ratio.
另外,作为在电化学元件为锂离子电容器的情况下优选使用的负极活性物质,可列举由上述碳形成的负极活性物质。In addition, as the negative electrode active material preferably used when the electrochemical element is a lithium ion capacitor, a negative electrode active material composed of the above-mentioned carbon is mentioned.
通常,对于电极活性物质的粒子的粒径,可以考虑到与电化学元件的其它构成要素之间的平衡而适当选择。其中,从提高初期效率、负荷特性、循环特性等电池特性的观点出发,电极活性物质的粒子体积基准D50平均粒径优选为1~50μm、更优选为15~30μm。In general, the particle size of the electrode active material particles can be appropriately selected in consideration of the balance with other constituent elements of the electrochemical device. Among them, from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics, the particle volume standard D50 average particle diameter of the electrode active material is preferably 1 to 50 μm, more preferably 15 to 30 μm.
从可以提高锂离子二次电池的容量、并且可以提高电极的柔软性、以及集电体和电极活性物质层之间的粘结性的观点出发,电极活性物质层中电极活性物质的含量优选为90~99.9重量%、更优选为95~99重量%。From the viewpoint that the capacity of the lithium ion secondary battery can be improved and the flexibility of the electrode can be improved and the binding property between the current collector and the electrode active material layer, the content of the electrode active material in the electrode active material layer is preferably 90 to 99.9% by weight, more preferably 95 to 99% by weight.
(导电剂)(conductive agent)
另外,作为本发明中根据需要而使用的导电剂,优选使用炉黑、乙炔黑(以下,也简称为“AB”)、及科琴黑(AkzoNobelChemicalsBesurotenFennotesshutup公司的注册商标)、碳纳米管、碳纳米角、石墨烯等导电性碳。在这些中,更优选乙炔黑。导电剂的平均粒径没有特别地限定,但从以较少的使用量发挥充分的导电性的观点出发,优选比电极活性物质的平均粒径小,优选为0.001~10μm、更优选为0.005~5μm、进一步优选为0.01~1μm。In addition, as the conductive agent used as needed in the present invention, furnace black, acetylene black (hereinafter also abbreviated as "AB"), Ketjen black (registered trademark of AkzoNobel Chemicals Besuroten Fennotesshutup), carbon nanotubes, carbon nano Conductive carbon such as horn and graphene. Among these, acetylene black is more preferred. The average particle size of the conductive agent is not particularly limited, but it is preferably smaller than the average particle size of the electrode active material, preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm, more preferably 0.01 to 1 μm.
在添加导电剂的情况下,导电剂的使用量相对于电极活性物质100重量份优选为1~10重量份、更优选为1~5重量份。When adding a conductive agent, the usage-amount of a conductive agent is preferably 1-10 weight part with respect to 100 weight part of electrode active materials, More preferably, it is 1-5 weight part.
(粒子复合体的制造方法)(Manufacturing method of particle complex)
粒子复合体可通过将电极用粘合剂、电极活性物质以及根据需要使用的导电剂进行干式混合而获得。这里所称的“干式混合”是指,使用混合机对电极用粘合剂、电极活性物质以及根据需要使用的导电剂进行混合,具体而言,是指以使混合时的固体成分浓度为99重量%以上的方式进行混合。作为具体的混合方法,可以列举:通过容器自身振荡、旋转、或振动来进行混合的、使用摇摆式混合机(RockingMixer)、转鼓混合机等的容器搅拌法;使用在相对于容器内水平或垂直的旋转轴上安装有用于搅拌的叶片、旋转盘或螺杆等的混合机,即水平圆筒型混合机、V型混合机、螺条式混合机、圆锥型螺杆混合机、高速流动型混合机、旋转圆盘型混合机以及高速旋转叶片混合机等的机械式搅拌;利用基于压缩气体的回旋气流的、在流化床中对粉体进行混合的气流搅拌等。另外,也可以使用将这些机构单独或组合使用而成的混合机。另外,也可以在进行干式混合之后,利用研钵等进行破碎至拆散凝聚的程度。通过进行干式混合,电化学元件电极用粒子复合体的分散被良好地保持,进而,涂布精度等各物性得到提高。The particle composite can be obtained by dry mixing an electrode binder, an electrode active material, and, if necessary, a conductive agent. The "dry mixing" referred to here means mixing the binder for electrodes, the electrode active material, and the conductive agent used if necessary using a mixer, and specifically means mixing so that the solid content concentration at the time of mixing is 99% by weight or more are mixed. As a specific mixing method, there may be mentioned: a container stirring method using a rocking mixer (Rocking Mixer), a drum mixer, etc., in which the container itself is oscillated, rotated, or vibrated; A mixer with a blade, a rotating disc or a screw for stirring is installed on the vertical rotating shaft, that is, a horizontal cylindrical mixer, a V-shaped mixer, a ribbon mixer, a conical screw mixer, and a high-speed flow type mixer. Mechanical agitation such as machines, rotating disc mixers, and high-speed rotary blade mixers; air agitation for mixing powders in a fluidized bed using swirling airflow based on compressed gas. Moreover, the mixer which used these mechanisms individually or in combination can also be used. In addition, after performing dry mixing, crushing may be carried out with a mortar or the like to the extent that aggregation is broken up. By performing dry mixing, the dispersion of the particle composite for electrochemical device electrodes is maintained well, and further, various physical properties such as coating accuracy are improved.
本发明的粒子复合体的体积基准D50平均粒径(Da)和电极活性物质的体积基准D50平均粒径(Db)之比(Da/Db)优选为0.5~2、更优选为0.8~2。即,优选多个电极活性物质未经复合化。The ratio (Da/Db) of the volume-based D50 average particle diameter (Da) of the particle composite of the present invention to the volume-based D50 average particle diameter (Db) of the electrode active material is preferably 0.5-2, more preferably 0.8-2. That is, it is preferable that a plurality of electrode active materials are not composited.
(电化学元件电极)(Electrochemical element electrodes)
本发明的电化学元件电极是将含有上述粒子复合体的电极活性物质层叠层在集电体上而成的电极。作为集电体的材料,例如,可以使用金属、碳、导电性高分子等,优选使用金属。作为金属,通常使用铜、铝、铂、镍、钽、钛、不锈钢、其他合金等。这些之中,从导电性、耐电压性的方面出发,优选使用铜、铝或铝合金。此外,在要求高耐电压性的情况下,可以优选使用在日本特开2001-176757号公报等中公开的高纯度的铝。集电体为膜或片状,其厚度可根据使用目的而适当选择,优选为1~200μm、更优选为5~100μm、进一步优选为10~50μm。The electrochemical element electrode of the present invention is an electrode obtained by laminating an electrode active material layer containing the above particle composite on a current collector. As the material of the current collector, for example, metal, carbon, conductive polymer, etc. can be used, and metal is preferably used. As the metal, copper, aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys, and the like are generally used. Among these, copper, aluminum, or an aluminum alloy is preferably used from the viewpoint of electrical conductivity and withstand voltage. In addition, when high voltage resistance is required, high-purity aluminum disclosed in JP-A-2001-176757 and the like can be preferably used. The current collector is in the form of a film or a sheet, and its thickness can be appropriately selected according to the purpose of use, and is preferably 1 to 200 μm, more preferably 5 to 100 μm, and still more preferably 10 to 50 μm.
将电极活性物质层叠层在集电体上时,可以将粒子复合体成型为片状、然后叠层在集电体上,但优选在集电体上直接加压成型粒子复合体的方法。作为进行加压成型的方法,可以列举例如:使用具备一对辊的辊式加压成型装置,在用辊传送集电体的同时,利用螺杆加料器等供给装置将粒子复合体供给至辊式加压成型装置,由此在集电体上成型电极活性物质层的辊加压成型法;将粒子复合体散布在集电体上,利用刮刀等将粒子复合体摊平以调整厚度,然后利用加压装置进行成型的方法;将粒子复合体填充在模具中,并对模具进行加压而成型的方法等。这其中,优选辊加压成型法。特别是,由于本发明的粒子复合体具有高流动性,因此能够在利用定量给料机进行供给、利用刮刀等使粉体层均一之后通过辊加压成型进行成型,由此可以提高生产性。When laminating the electrode active material layer on the current collector, the particle composite may be formed into a sheet and then laminated on the current collector, but a method of directly press-molding the particle composite on the current collector is preferable. As a method of press molding, for example, using a roll press molding device equipped with a pair of rolls, while conveying the current collector with the rolls, the particle composite is supplied to the roll press by a supply device such as a screw feeder. Pressure molding device, whereby the roller pressure molding method of forming the electrode active material layer on the current collector; the particle composite is spread on the current collector, and the particle composite is flattened with a scraper to adjust the thickness, and then used A method of molding with a pressurizing device; a method of filling a particle composite in a mold and pressurizing the mold to form it; and the like. Among them, the roll press molding method is preferable. In particular, since the particle composite of the present invention has high fluidity, it can be formed by roll press molding after being supplied by a quantitative feeder, uniformizing the powder layer by a doctor blade, etc., thereby improving productivity.
就进行辊加压成型时的辊温度而言,从能够使电极活性物质层与集电体之间的密合性充分的观点出发,优选为25~200℃、更优选为50~150℃、进一步优选为80~120℃。此外,作为辊加压成型时的辊间的压制线压,从能够提高电极活性物质层的厚度的均一性的观点出发,优选为10~1000kN/m、更优选为200~900kN/m、进一步优选为300~600kN/m。此外,辊加压成型时的成型速度优选为0.1~20m/分钟、更优选为4~10m/分钟。The roll temperature during roll press molding is preferably 25 to 200° C., more preferably 50 to 150° C., from the viewpoint of enabling sufficient adhesion between the electrode active material layer and the current collector. More preferably, it is 80-120 degreeC. In addition, as the pressing linear pressure between the rolls during roll press molding, from the viewpoint of being able to improve the uniformity of the thickness of the electrode active material layer, it is preferably 10 to 1000 kN/m, more preferably 200 to 900 kN/m, and furthermore Preferably it is 300 to 600 kN/m. In addition, the molding speed during roll press molding is preferably 0.1 to 20 m/min, more preferably 4 to 10 m/min.
此外,为了使成型的电化学元件电极的厚度没有偏差,提高电极活性物质层的密度,从而谋求高容量化,可以根据需要进一步进行后加压。后加压的方法优选利用辊进行的加压工序。在辊加压工序中,通过将2根圆柱状的辊以狭窄的间隔平行地上下排列,使各自向相反的方向旋转,并在其间夹持电极,由此进行加压。此时,根据需要,也可以对辊进行加热或冷却等温度调节。In addition, post-pressurization may be further performed as necessary in order to increase the density of the electrode active material layer without variation in the thickness of the electrode of the formed electrochemical element and to increase the capacity. The method of post-pressurization is preferably a pressurization step using a roller. In the roller pressing step, two columnar rollers are arranged vertically in parallel at a narrow interval, each rotates in opposite directions, and the electrode is sandwiched between them, thereby applying pressure. At this time, temperature adjustment such as heating or cooling of the roll may be performed as necessary.
(电化学元件)(electrochemical components)
本发明的电化学元件将如上所述得到的电化学元件电极用于正极和负极中的至少一者,并进一步具备隔板及电解液。作为电化学元件,可列举例如锂离子二次电池、锂离子电容器等。The electrochemical element of the present invention uses the electrochemical element electrode obtained as described above as at least one of a positive electrode and a negative electrode, and further includes a separator and an electrolytic solution. As an electrochemical element, a lithium ion secondary battery, a lithium ion capacitor, etc. are mentioned, for example.
(隔板)(partition)
作为隔板,可以使用包含聚乙烯、聚丙烯等聚烯烃树脂、芳香族聚酰胺树脂的微孔膜或无纺布;包含无机陶瓷粉末的多孔性树脂涂层等。作为具体例,可以举出:由聚烯烃类(聚乙烯、聚丙烯、聚丁烯、聚氯乙烯)、以及它们的混合物或共聚物等树脂形成的微多孔膜;由聚对苯二甲酸乙二醇酯、聚环烯烃、聚醚砜、聚酰胺、聚酰亚胺、聚酰亚胺酰胺、聚芳酰胺、聚环烯烃、尼龙、聚四氟乙烯等树脂形成的微多孔膜;编织聚烯烃类的纤维而成的材料或其无纺布;绝缘性物质粒子的聚集体等。这些之中,由于可以减薄隔板整体的膜厚,增加锂离子二次电池内的活性物质比率,从而提高每单位体积的容量,因此优选由聚烯烃类的树脂形成的微多孔膜。As the separator, a microporous film or nonwoven fabric made of polyolefin resin such as polyethylene or polypropylene, or aromatic polyamide resin; a porous resin coating made of inorganic ceramic powder; and the like can be used. Specific examples include: microporous membranes made of polyolefins (polyethylene, polypropylene, polybutylene, polyvinyl chloride) and their mixtures or copolymers; polyethylene terephthalate Microporous membranes made of glycol ester, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimide amide, polyaramid, polycycloolefin, nylon, polytetrafluoroethylene and other resins; braided poly Materials made of olefin fibers or non-woven fabrics; aggregates of insulating material particles, etc. Among these, a microporous film formed of a polyolefin resin is preferable because it can reduce the film thickness of the entire separator and increase the active material ratio in the lithium ion secondary battery, thereby increasing the capacity per unit volume.
就隔板的厚度而言,从能够减小锂离子二次电池中由隔板引起的内部电阻的观点、以及在制造锂离子二次电池时的作业性优异的观点出发,优选为0.5~40μm、更优选为1~30μm、进一步优选为1~25μm。The thickness of the separator is preferably 0.5 to 40 μm from the viewpoint of reducing the internal resistance caused by the separator in the lithium ion secondary battery and from the viewpoint of excellent workability when manufacturing the lithium ion secondary battery , more preferably 1 to 30 μm, still more preferably 1 to 25 μm.
(电解液)(electrolyte)
作为锂离子二次电池用的电解液,例如可使用在非水溶剂中溶解支持电解质而成的非水电解液。作为支持电解质,优选采用锂盐。作为锂盐,可以列举例如:LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLi等。其中,优选容易溶解在溶剂中且显示高解离度的LiPF6、LiClO4、CF3SO3Li。这些可以单独使用1种,也可以以任意的比例组合使用2种以上。使用解离度越高的支持电解质则锂离子电导率越高,因此,可以根据支持电解质的种类来调节锂离子电导率。As the electrolytic solution for lithium ion secondary batteries, for example, a nonaqueous electrolytic solution obtained by dissolving a supporting electrolyte in a nonaqueous solvent can be used. As the supporting electrolyte, lithium salts are preferably used. Examples of lithium salts include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 )NLi, etc. Among them, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable, which are easily dissolved in a solvent and exhibit a high degree of dissociation. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. The use of a supporting electrolyte with a higher degree of dissociation leads to a higher lithium ion conductivity. Therefore, the lithium ion conductivity can be adjusted according to the type of supporting electrolyte.
就电解液中的支持电解质的浓度而言,优选根据支持电解质的种类、以0.5~2.5mol/L的浓度使用。支持电解质的浓度过低或过高均存在导致离子电导度降低的可能性。The concentration of the supporting electrolyte in the electrolytic solution is preferably used at a concentration of 0.5 to 2.5 mol/L depending on the type of supporting electrolyte. Too low or too high a concentration of supporting electrolyte may lead to a decrease in ion conductivity.
作为非水溶剂,只要为能够溶解支持电解质的溶剂就没有特别限定。作为非水溶剂的例子,可以列举:碳酸二甲酯(DMC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸甲乙酯(MEC)等碳酸酯类;γ-丁内酯、甲酸甲酯等酯类;1,2-二甲氧基乙烷、四氢呋喃等醚类;环丁砜、二甲亚砜等含硫化合物类;也被用作支持电解质的离子液体等。其中,由于介电常数高、稳定的电位范围宽,因此优选碳酸酯类。非水溶剂可以单独使用1种,也可以以任意比例组合使用2种以上。一般地,非水溶剂的粘度越低则锂离子电导率越高,介电常数越高则支持电解质的溶解度越高,但两者处于折衷(tradeoff)的关系,因此可以根据溶剂的种类、混合比来调节锂离子电导率而使用。此外,非水溶剂可以组合使用或整体使用全部或部分氢被氟取代而成的溶剂。The non-aqueous solvent is not particularly limited as long as it can dissolve the supporting electrolyte. As the example of nonaqueous solvent, can enumerate: Dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), carbonic acid Carbonates such as methyl ethyl ester (MEC); Esters such as γ-butyrolactone and methyl formate; Ethers such as 1,2-dimethoxyethane and tetrahydrofuran; Sulfur-containing compounds such as sulfolane and dimethyl sulfoxide Classes; also used as ionic liquids for supporting electrolytes, etc. Among them, carbonates are preferable because they have a high dielectric constant and a wide stable potential range. The non-aqueous solvent may be used alone or in combination of two or more in any ratio. Generally, the lower the viscosity of the non-aqueous solvent, the higher the lithium ion conductivity, and the higher the dielectric constant, the higher the solubility of the supporting electrolyte, but the two are in a tradeoff relationship, so it can be determined according to the type of solvent, mixing Ratio is used to adjust the lithium ion conductivity. In addition, as the non-aqueous solvent, a solvent in which all or part of hydrogen is substituted by fluorine may be used in combination or as a whole.
此外,电解液中也可以含有添加剂。作为添加剂,例如可以举出:碳酸亚乙烯酯(VC)等碳酸酯类化合物;亚硫酸亚乙酯(ES)等含硫化合物;氟代碳酸亚乙酯(FEC)等含氟化合物。添加剂可单独使用1种,也可以以任意的比率组合使用2种以上。In addition, additives may also be contained in the electrolytic solution. Examples of additives include carbonate-based compounds such as vinylene carbonate (VC); sulfur-containing compounds such as ethylene sulfite (ES); and fluorine-containing compounds such as fluoroethylene carbonate (FEC). An additive may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.
需要说明的是,作为锂离子电容器用的电解液,可以使用与上述的可用于锂离子二次电池的电解液同样的电解液。In addition, as an electrolytic solution for lithium ion capacitors, the same electrolytic solution as the electrolytic solution which can be used for a lithium ion secondary battery mentioned above can be used.
(电化学元件的制造方法)(Manufacturing method of electrochemical device)
作为锂离子二次电池、锂离子电容器等电化学元件的具体的制造方法,例如可以列举如下方法:隔着隔板叠合正极和负极,并将其根据电池形状卷曲、弯折等后放入电池容器,向电池容器注入电解液并封口。进一步,也可以根据需要而放入膨胀合金;保险丝、PTC元件等过电流防止元件;引线板等,从而防止电池内部的压力升高、过充放电。锂离子二次电池的形状可以为硬币型、纽扣型、片型、圆筒型、方型、扁平型等中的任意形状。就电池容器的材质而言,只要是能够阻碍水分侵入电池内部的材质即可,不特别限定于金属制、铝等的层压材料制等。As a specific method of manufacturing electrochemical elements such as lithium-ion secondary batteries and lithium-ion capacitors, for example, the method of laminating a positive electrode and a negative electrode through a separator, curling, bending, etc. according to the shape of the battery, and putting them in The battery container is filled with electrolyte solution and sealed. Furthermore, expansion alloys; overcurrent prevention elements such as fuses and PTC elements; lead plates, etc. may be added as needed to prevent pressure rise inside the battery and overcharge and discharge. The shape of the lithium ion secondary battery may be any shape among coin type, button type, sheet type, cylindrical type, square type, flat type and the like. The material of the battery container is not particularly limited to a material made of metal, a laminated material such as aluminum, or the like, as long as it can prevent moisture from entering the battery.
根据本实施方式的电化学元件电极用粘合剂,电极的生产性优异,得到的电极的厚度精度及柔软性良好。此外,由于本发明的电化学元件电极不使用羧甲基纤维素等分散剂,因此能够降低得到的电化学元件的电阻。According to the binder for electrochemical element electrodes of this embodiment, the productivity of an electrode is excellent, and the thickness precision and flexibility of the obtained electrode are favorable. In addition, since the electrochemical element electrode of the present invention does not use a dispersant such as carboxymethyl cellulose, the electrical resistance of the obtained electrochemical element can be reduced.
另外,通过使电极用粘合剂的玻璃化转变温度在给定的范围,即使是得到的粒子复合体为小粒径也可以确保流动性,因此能够确保电极的厚度精度。进一步,通过使电化学元件电极用粘合剂的玻璃化转变温度在给定的范围,可以确保得到的电极的强度和柔软性。In addition, by setting the glass transition temperature of the electrode binder within a predetermined range, fluidity can be ensured even if the obtained particle composite has a small particle size, so that the thickness accuracy of the electrode can be ensured. Furthermore, by setting the glass transition temperature of the binder for electrochemical element electrodes within a predetermined range, the strength and flexibility of the resulting electrode can be ensured.
另外,由于在得到粒子复合体时不使用浆料,因此可以减少制造所耗费的能量。进一步,由于连续操作容易,因此可以提高成品率。In addition, since no slurry is used to obtain the particle composite, energy consumed for production can be reduced. Furthermore, since continuous operation is easy, yield can be improved.
实施例Example
以下,结合实施例对本发明具体地进行说明,但本发明并不限定于以下所示的实施例,可以在不超过本发明的要旨及其均等的范围的范围内任意地变更来实施。需要说明的是,在以下的说明中,表示量的“%”及“份”只要没有特别说明,则为重量基准。Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples shown below, and can be implemented with arbitrary changes within a range not exceeding the gist of the present invention and its equivalent range. In addition, in the following description, unless otherwise indicated, "%" and "part" which show an amount are based on weight.
在实施例及比较例中,分别如下地进行了电极用粘合剂(负极用粘合剂或正极用粘合剂)的玻璃化转变温度(Tg)的测定、初级粒子的体积基准D50平均粒径(初级粒径)的测定、粒子复合体的体积基准D50平均粒径(Da)以及电极活性物质的体积基准D50平均粒径(Db)的测定、电极用粘合剂的120℃挥发成分测定、电极用粘合剂的最低制膜温度的测定及电极用粘合剂的形状测定。In Examples and Comparative Examples, the measurement of the glass transition temperature (Tg) of the electrode binder (the binder for the negative electrode or the binder for the positive electrode), the volume standard D50 average particle size of the primary particles, and Measurement of diameter (primary particle diameter), volume-based D50 average particle diameter (Da) of particle complexes and volume-based D50 average particle diameter (Db) of electrode active materials, measurement of 120°C volatile components of electrode binders , Measurement of the minimum film-forming temperature of the electrode binder and shape measurement of the electrode binder.
<玻璃化转变温度><Glass transition temperature>
电极用粘合剂的玻璃化转变温度(Tg)使用差示扫描量热仪(Nanotechnology公司制DSC6220SII)、基于JISK7121:1987进行了测定。The glass transition temperature (Tg) of the binder for electrodes was measured based on JISK7121:1987 using the differential scanning calorimeter (DSC6220SII by the Nanotechnology company).
<初级粒径的测定><Measurement of Primary Particle Size>
向直链烷基苯磺酸钠的1%水溶液中分别添加实施例及比较例制造的电极用粘合剂(负极用粘合剂1~12、正极用粘合剂1~13),利用超声波进行分散化,然后基于利用CoulterCounterLS230(Coulter公司制粒径测定器)而得到的累积粒径分布进行测定,将相当于其50%累积值的粒径作为电极用粘合剂的体积基准D50平均粒径(初级粒径)。Add the binders for electrodes (1-12 for negative electrodes, 1-13 for positive electrodes) produced in the examples and comparative examples to the 1% aqueous solution of sodium linear alkylbenzene sulfonate, respectively, and use ultrasonic Disperse, then measure based on the cumulative particle size distribution obtained by Coulter Counter LS230 (a particle size measuring device manufactured by Coulter Co.), and use the particle size corresponding to 50% of the cumulative value as the volume standard D50 average particle size of the electrode binder diameter (primary particle size).
<Da和Db的测定><Measurement of Da and Db>
基于利用激光衍射/散射式粒度分布测定装置(MicrotracMT3200II;日机装)得到的干式的累积粒径分布测定了实施例及比较例中制造的粒子复合体的体积基准D50平均粒径(Da)、和实施例及比较例中使用的电极活性物质的体积基准D50平均粒径(Db),求出了比(Da/Db)。The volume-based D50 average particle diameter (Da) of the particle complexes produced in Examples and Comparative Examples was measured based on the dry-type cumulative particle size distribution obtained by a laser diffraction/scattering particle size distribution measuring device (Microtrac MT3200II; Nikkiso). , and the volume-based D50 average particle diameter (Db) of the electrode active materials used in Examples and Comparative Examples were used to obtain the ratio (Da/Db).
<120℃挥发成分的测定><Determination of volatile components at 120°C>
在设定为120℃的烘箱内分别放入实施例及比较例中制造的粉末状负极用粘合剂1~12、粉末状正极用粘合剂1~13,每10分钟进行粘合剂重量的测定,在重量变化达到低于0.1%的时刻终止测定。将此时的从初期重量起到测定终止时为止的重量变化率(减少的比例)作为120℃挥发成分。Put the binders 1 to 12 for negative electrodes in powder form and binders 1 to 13 for positive electrodes in powder form produced in Examples and Comparative Examples in an oven set at 120°C, and measure the weight of the binders every 10 minutes. The determination was terminated when the weight change reached less than 0.1%. Let the weight change rate (ratio of decrease) from the initial weight at this time until the end of measurement be 120 degreeC volatile matter.
<最低制膜温度><Minimum film forming temperature>
使用最低制膜温度测定装置(MFFTB90;RHOPOINT公司制)、依据ISO2115进行了试验。The test was performed in accordance with ISO2115 using a minimum film forming temperature measuring device (MFFTB90; manufactured by RHOPOINT).
<形状测定><Shape measurement>
利用SEM观察粉末状电极用粘合剂,随机取出图像中观察到的粒子30个,求出各个粒子的平均短轴直径、平均长轴直径,并算出平均球形度。将此时平均球形度为80%以上的情况视为球状、平均球形度低于80%的粒子视为非球状。The powdery electrode binder was observed by SEM, 30 particles observed in the image were randomly taken out, the average minor axis diameter and the average major axis diameter of each particle were obtained, and the average sphericity was calculated. At this time, particles with an average sphericity of 80% or more were regarded as spherical, and particles with an average sphericity of less than 80% were regarded as non-spherical.
此外,在实施例及比较例中,分别如下地进行了电极精度、电极的柔软性及速率特性的评价。In addition, in Examples and Comparative Examples, evaluations of electrode accuracy, flexibility of electrodes, and rate characteristics were performed as follows.
<电极精度><Electrode Accuracy>
针对在实施例及比较例中制作的电极活性物质层的TD方向(横向)上10cm、MD方向(纵向)上10cm,测定了在TD方向上均等地取3点、在MD方向上均等地取3点的、共计9点的膜厚。将该膜厚的平均值设为A、将距离平均值最远的厚度设为B时,利用下式计算了电极厚度偏差。For 10 cm in the TD direction (lateral direction) and 10 cm in the MD direction (longitudinal) of the electrode active material layers produced in Examples and Comparative Examples, 3 points were taken equally in the TD direction, and 10 cm in the MD direction were taken equally. 3 points, a total of 9 points of film thickness. When the average value of the film thickness is A and the thickness farthest from the average value is B, the electrode thickness variation was calculated by the following formula.
电极厚度偏差精度(%)=(|A-B|)×100/AElectrode thickness deviation accuracy (%)=(|A-B|)×100/A
将其作为电极精度,利用以下的基准进行了评价。结果如表1及表2所示。该值越小表示成型性越优异。This was evaluated as electrode accuracy by the following criteria. The results are shown in Table 1 and Table 2. The smaller the value, the better the formability.
A:低于4%A: Less than 4%
B:4%以上且低于9%B: More than 4% and less than 9%
C:9%以上且低于15%C: More than 9% and less than 15%
D:15%以上D: more than 15%
E:电极上有孔E: There are holes in the electrode
<电极的柔软性><Flexibility of electrodes>
将实施例及比较例中制作的电化学元件电极切成1cm×8cm,分别卷绕于直径3mm、4mm、5mm的金属棒,对于产生的裂纹如下地进行了评价。结果如表1及表2所示。裂纹越少表示柔软性越优异,即表示电极强度越优异。The electrochemical element electrodes produced in Examples and Comparative Examples were cut into 1 cm×8 cm, wound around metal rods with diameters of 3 mm, 4 mm, and 5 mm, respectively, and the occurrence of cracks was evaluated as follows. The results are shown in Table 1 and Table 2. The smaller the number of cracks, the better the flexibility, that is, the better the electrode strength.
A:在直径3mm的金属棒上没有裂纹A: There is no crack on the metal rod with a diameter of 3mm
B:在直径4mm的金属棒上没有裂纹,但在直径3mm的金属棒上存在裂纹B: There are no cracks on the metal rod with a diameter of 4mm, but there are cracks on the metal rod with a diameter of 3mm
C:在直径5mm的金属棒上存在裂纹C: There are cracks on the metal rod with a diameter of 5 mm
<速率特性><rate characteristic>
对于实施例及比较例中制作的层压单元型的锂离子二次电池,在电解液注液后,静置5小时,在25℃气体氛围中通过0.2C的恒流法充电至电池电压为3.65V,然后升温至60℃,进行12小时熟化处理,于25℃气体氛围中通过0.2C的恒流法放电至电池电压为3.00V。For the laminated unit type lithium-ion secondary battery made in the embodiment and the comparative example, after the electrolyte solution was injected, it was left to stand for 5 hours, and charged to a battery voltage of 3.65V, then raise the temperature to 60°C, carry out aging treatment for 12 hours, and discharge to the battery voltage of 3.00V by 0.2C constant current method in 25°C gas atmosphere.
然后,在25℃气体氛围中,以4.2V、0.2C速率进行了充电、以0.2C及2.0C速率进行了放电。此时,将各放电速率时的放电容量定义为C0.2(0.2C时的放电容量)、C2.0(2.0C时的放电容量),求出以ΔC=C2.0/C0.2时的放电容量×100(%)表示的容量变化率,并按照以下的基准进行了评价。结果如表1及表2所示。该容量变化率ΔC的值越高,表示放电速率特性(速率特性)越优异。Then, in a gas atmosphere at 25° C., charging was performed at 4.2 V at a rate of 0.2 C, and discharge was performed at a rate of 0.2 C and 2.0 C. At this time, the discharge capacity at each discharge rate is defined as C 0.2 (discharge capacity at 0.2C), C 2.0 (discharge capacity at 2.0C), and the discharge capacity at ΔC=C 2.0 /C 0.2 × The rate of change in capacity represented by 100(%) was evaluated according to the following criteria. The results are shown in Table 1 and Table 2. The higher the value of the capacity change rate ΔC, the better the discharge rate characteristic (rate characteristic).
A:ΔC为83%以上A: ΔC is 83% or more
B:ΔC为82%以上且低于83%B: ΔC is 82% or more and less than 83%
C:ΔC为80%以上且低于82%C: ΔC is 80% or more and less than 82%
D:ΔC低于80%D: ΔC below 80%
<实施例1><Example 1>
(负极用粒子状聚合物1的制造)(Manufacture of Particulate Polymer 1 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯(以下也简称为“ST”)78份、1,3-丁二烯(以下也简称为“BD”)19份、衣康酸(以下也简称为“IA”)3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DowChemical公司制)以固体成分当量计0.4份、离子交换水150份、作为链转移剂的叔十二烷基硫醇(以下也简称为“TDM”)0.3份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物1(苯乙烯-丁二烯共聚物;以下也简称为“SBR”)的水分散体。负极用粒子状聚合物1的最低制膜温度为55℃、玻璃化转变温度(Tg)为50℃、初级粒径为132nm。Add 78 parts of styrene (hereinafter referred to as "ST"), 19 parts of 1,3-butadiene (hereinafter referred to as "BD"), itaconic acid (hereinafter referred to as 3 parts of "IA"), 0.4 parts of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by Dow Chemical Co., Ltd.) as an emulsifier, 150 parts of ion-exchanged water, 0.3 parts of tert-dodecyl mercaptan (hereinafter also referred to as "TDM") as an agent and 0.5 parts of potassium persulfate as a polymerization initiator were sufficiently stirred and then heated to 75° C. to initiate polymerization. When the polymerization conversion rate reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the negative electrode particulate polymer 1 (styrene-butadiene copolymer; hereinafter also abbreviated as "SBR") was obtained. The minimum film forming temperature of the particulate polymer 1 for negative electrodes was 55° C., the glass transition temperature (Tg) was 50° C., and the primary particle diameter was 132 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物1的水分散体中除去水分,然后利用真空干燥机在40℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物1,得到了粉末状的负极用粘合剂1。粉末状的负极用粘合剂1的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 1 for negative electrodes at 40° C. by a rotary evaporator, and then dried by a vacuum dryer at 40° C. and 0.6 kPa. Then, the dried particulate polymer 1 for negative electrodes was crushed with a mortar to obtain a powdery binder 1 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 1 was 0.1%.
(粒子复合体的制造)(Manufacture of particle complexes)
将作为负极活性物质的人造石墨(平均粒径:24.5μm、石墨层间距(基于X射线衍射法测定的(002)面的面间隔(d值)):0.354nm)98.8份、以及上述负极用粘合剂以固体成分换算量计1.2份,使用亨舍尔混合机(三井三池公司制)混合10分钟,使负极用粘合剂附着于负极活性物质,得到了粒子复合体。98.8 parts of artificial graphite (average particle size: 24.5 μm, distance between graphite layers (interplanar distance (d value) of (002) plane measured based on X-ray diffraction method): 0.354 nm) as the negative electrode active material, and the above-mentioned negative electrode The binder was 1.2 parts in terms of solid content, and was mixed for 10 minutes using a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.), and the negative electrode binder was attached to the negative electrode active material to obtain a particle composite.
(负极的制造)(manufacture of negative electrode)
使用定量给料机(Nikka公司制“NikkasprayK-V”)将上述得到的粒子复合体供给至辊压机(HIRANOGIKENKOGYO公司制“剪切粗面热辊”)的压制用辊(辊温度100℃、压制线压500kN/m)。在压制用辊间插入厚度20μm的铜箔,使从定量给料机供给的上述粒子复合体附着在铜箔上,以成型速度1.5m/分钟进行加压成型,得到了具有负极活性物质的负极。The particle composite obtained above was supplied to the pressing roll (roll temperature 100° C., 100° C., Compression line pressure 500kN/m). Copper foil with a thickness of 20 μm was inserted between pressing rolls, and the above-mentioned particle composite supplied from a quantitative feeder was attached to the copper foil, and press-molded at a molding speed of 1.5 m/min to obtain a negative electrode having a negative electrode active material. .
(正极用浆料以及正极的制造)(Manufacture of positive electrode slurry and positive electrode)
向作为正极活性物质的LiCoO292份中加入作为正极用粘合剂的聚偏氟乙烯(PVDF;KurehaChemical公司制“KF-1100”)、并使固体成分量达到2份,然后,加入乙炔黑(电气化学工业公司制“HS-100”)6份、N-甲基吡咯烷酮20份,利用行星式混合机进行混合,得到了正极用浆料。将该正极用浆料涂布于厚度18μm的铝箔,于120℃干燥30分钟后,进行辊压,得到了厚度60μm的正极。Add polyvinylidene fluoride (PVDF; "KF-1100" manufactured by Kureha Chemical Co., Ltd.) as a binder for positive electrodes to 92 parts of LiCoO 2 as a positive electrode active material so that the amount of solid content becomes 2 parts, and then add acetylene black ("HS-100" manufactured by Denki Kagaku Kogyo Co., Ltd.) 6 parts and 20 parts of N-methylpyrrolidone were mixed with a planetary mixer to obtain a positive electrode slurry. This positive electrode slurry was applied to an aluminum foil with a thickness of 18 μm, dried at 120° C. for 30 minutes, and then rolled to obtain a positive electrode with a thickness of 60 μm.
(隔板的准备)(Preparation of partitions)
将单层的聚丙烯制隔板(宽65mm、长500mm、厚25μm,利用干式法制造,气孔率55%)冲切为5×5cm2的正方形。A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by a dry method, porosity 55%) was punched out into a square of 5×5 cm 2 .
(锂离子二次电池的制造)(manufacture of lithium-ion secondary batteries)
作为电池的外包装,准备了铝外包装材料。将上述得到的正极冲切为4×4cm2的正方形,以使集电体侧的表面与铝外包装材料接触的方式进行了配置。另外,在上述得到的正极的正极活性物质层的面上配置了上述得到的正方形的隔板。然后,将上述得到的负极切成4.2×4.2cm2的正方形,以使负极活性物质层侧的表面面向隔板的方式配置在隔板上。进一步,填充了含有2.0%的碳酸亚乙烯酯的、浓度为1.0M的LiPF6溶液。该LiPF6溶液的溶剂为碳酸亚乙酯(EC)和碳酸甲乙酯(EMC)的混合溶剂(EC/EMC=3/7(体积比))。进而,为了将铝包装材料的开口密封,于150℃进行热封而将铝外包装封口,制造了层压型的锂离子二次电池(层压型电池)。As the outer packaging of the battery, an aluminum outer packaging material was prepared. The positive electrode obtained above was punched out into a square of 4×4 cm 2 , and arranged so that the surface on the collector side was in contact with the aluminum exterior material. Moreover, the square separator obtained above was arrange|positioned on the surface of the positive electrode active material layer of the positive electrode obtained above. Then, the negative electrode obtained above was cut into a square of 4.2×4.2 cm 2 , and placed on the separator so that the surface on the side of the negative electrode active material layer faced the separator. Further, a LiPF 6 solution having a concentration of 1.0 M containing 2.0% of vinylene carbonate was filled. The solvent of the LiPF 6 solution is a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (EC/EMC=3/7 (volume ratio)). Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing was performed at 150 degreeC, and the aluminum outer package was sealed, and the laminated type lithium ion secondary battery (laminated type battery) was manufactured.
<实施例2><Example 2>
(负极用粒子状聚合物2的制造)(Manufacture of Particulate Polymer 2 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯74.5份、1,3-丁二烯22.5份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、离子交换水150份、作为链转移剂的叔十二烷基硫醇0.3份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物2的水分散体。粒子状聚合物2的最低制膜温度为40℃,玻璃化转变温度(Tg)为40℃,初级粒径为135nm。Add 74.5 parts of styrene, 22.5 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Company) 0.4 parts in terms of solid content equivalents, 150 parts of ion-exchanged water, 0.3 parts of tertiary dodecyl mercaptan as a chain transfer agent, and 0.5 parts of potassium persulfate as a polymerization initiator, fully stirred Then, it was heated to 75° C. to initiate polymerization. When the polymerization conversion rate reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the particulate polymer 2 for negative electrodes was obtained. The minimum film forming temperature of the particulate polymer 2 was 40°C, the glass transition temperature (Tg) was 40°C, and the primary particle diameter was 135 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于25℃从上述负极用粒子状聚合物2的水分散体中除去水分,然后利用真空干燥机在25℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物2,得到了粉末状的负极用粘合剂2。粉末状的负极用粘合剂2的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 2 for negative electrodes at 25° C. by a rotary evaporator, and dried by a vacuum dryer at 25° C. and 0.6 kPa. Then, the dried particulate polymer 2 for negative electrodes was crushed with a mortar to obtain a powdery binder 2 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 2 was 0.1%.
除了使用了上述负极用粘合剂2之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 2 for negative electrodes was used.
<实施例3><Example 3>
(负极用粒子状聚合物3的制造)(Manufacture of Particulate Polymer 3 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯85份、1,3-丁二烯12份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、离子交换水150份、作为链转移剂的叔十二烷基硫醇0.3份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物3的水分散体。负极用粒子状聚合物3的最低制膜温度为88℃,玻璃化转变温度(Tg)为70℃,初级粒径为134nm。Add 85 parts of styrene, 12 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Company) 0.4 parts in terms of solid content equivalents, 150 parts of ion-exchanged water, 0.3 parts of tertiary dodecyl mercaptan as a chain transfer agent, and 0.5 parts of potassium persulfate as a polymerization initiator, fully stirred Then, it was heated to 75° C. to initiate polymerization. When the polymerization conversion ratio reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the particulate polymer 3 for negative electrodes was obtained. The minimum film forming temperature of the negative electrode particulate polymer 3 was 88°C, the glass transition temperature (Tg) was 70°C, and the primary particle diameter was 134 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于60℃从上述负极用粒子状聚合物3的水分散体中除去水分,然后利用真空干燥机在60℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物3,得到了粉末状的负极用粘合剂3。粉末状的负极用粘合剂3的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 3 for negative electrodes at 60° C. by a rotary evaporator, and dried by a vacuum dryer at 60° C. and 0.6 kPa. Then, the dried particulate polymer 3 for negative electrodes was crushed with a mortar to obtain powdery binder 3 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 3 was 0.1%.
除了使用了上述负极用粘合剂3之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 1 except that the above-mentioned binder 3 for negative electrodes was used.
<实施例4><Example 4>
(负极用粒子状聚合物4的制造)(Manufacture of Particulate Polymer 4 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯78份、1,3-丁二烯19份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计2.0份、离子交换水150份、作为链转移剂的叔十二烷基硫醇0.3份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物4的水分散体。负极用粒子状聚合物4的最低制膜温度为53℃,玻璃化转变温度(Tg)为50℃,初级粒径为80nm。Add 78 parts of styrene, 19 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Company) 2.0 parts by solid content equivalent, 150 parts of ion-exchanged water, 0.3 parts of tertiary dodecyl mercaptan as a chain transfer agent, and 0.5 parts of potassium persulfate as a polymerization initiator, fully stirred Then, it was heated to 75° C. to initiate polymerization. When the polymerization conversion ratio reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the particulate polymer 4 for negative electrodes was obtained. The minimum film forming temperature of the negative electrode particulate polymer 4 is 53°C, the glass transition temperature (Tg) is 50°C, and the primary particle diameter is 80nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物4的水分散体中除去水分,然后利用真空干燥机在40℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物4,得到了粉末状的负极用粘合剂4。粉末状的负极用粘合剂4的120℃挥发成分为0.4%。Moisture was removed from the aqueous dispersion of the particulate polymer 4 for negative electrodes at 40° C. by a rotary evaporator, and dried by a vacuum dryer at 40° C. and 0.6 kPa. Then, the dried particulate polymer 4 for negative electrodes was crushed with a mortar to obtain powdery binder 4 for negative electrodes. The 120° C. volatile content of the powdery negative electrode binder 4 was 0.4%.
除了使用了上述负极用粘合剂4之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 1 except that the above-mentioned binder 4 for negative electrodes was used.
<实施例5><Example 5>
(负极用粒子状聚合物5的制造)(Manufacture of Particulate Polymer 5 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入离子交换水210份,边搅拌边加热至75℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向与上述不同的另外的带搅拌机的5MPa耐压容器中加入苯乙烯78份、1,3-丁二烯19份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、作为链转移剂的叔十二烷基硫醇0.3份、及离子交换水26份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经3.5小时以恒定的速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了负极用粒子状聚合物5的水分散体。负极用粒子状聚合物5的最低制膜温度为56℃,玻璃化转变温度(Tg)为50℃,初级粒径为304nm。210 parts of ion-exchanged water were added to a 5 MPa pressure-resistant container equipped with a stirrer, heated to 75°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, add 78 parts of styrene, 19 parts of 1,3-butadiene, 3 parts of itaconic acid, and alkyl diphenyl ether disulfone Salt (DOWFAX (registered trademark) 2A1, DOWChemical company make) 0.4 parts in terms of solid content equivalents, 0.3 parts of tert-dodecyl mercaptan as chain transfer agent, and 26 parts of ion-exchanged water, it is stirred and emulsified, Thus, a monomer mixed liquid was prepared. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 3.5 hours, so that This was reacted until the polymerization conversion rate reached 95%, and the aqueous dispersion of the particulate polymer 5 for negative electrodes was obtained. The minimum film-forming temperature of the negative electrode particulate polymer 5 was 56° C., the glass transition temperature (Tg) was 50° C., and the primary particle diameter was 304 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物5的水分散体中除去水分,然后利用真空干燥机在40℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物5,得到了粉末状的负极用粘合剂5。粉末状的负极用粘合剂5的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 5 for negative electrodes at 40° C. by a rotary evaporator, and dried by a vacuum dryer at 40° C. and 0.6 kPa. Then, the dried particulate polymer 5 for negative electrodes was crushed with a mortar to obtain powdery binder 5 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 5 was 0.1%.
除了使用了上述负极用粘合剂5之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 5 for negative electrodes was used.
<实施例6><Example 6>
(负极用粒子状聚合物6的制造)(Manufacture of Particulate Polymer 6 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入离子交换水210份,边搅拌边加热至75℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向与上述不同的另外的带搅拌机的5MPa耐压容器中加入苯乙烯78份、1,3-丁二烯19份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.2份、作为链转移剂的叔十二烷基硫醇0.3份、及离子交换水26份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经3.5小时以恒定的速度,添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了负极用粒子状聚合物6的水分散体。负极用粒子状聚合物6的最低制膜温度为56℃,玻璃化转变温度(Tg)为50℃,初级粒径为625nm。210 parts of ion-exchanged water were added to a 5 MPa pressure-resistant container equipped with a stirrer, heated to 75°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, add 78 parts of styrene, 19 parts of 1,3-butadiene, 3 parts of itaconic acid, and alkyl diphenyl ether disulfone Salt (DOWFAX (registered trademark) 2A1, DOWChemical company make) 0.2 parts in terms of solid content equivalents, 0.3 parts of tertiary dodecyl mercaptan as chain transfer agent, and 26 parts of ion-exchanged water, it is stirred and emulsified, Thus, a monomer mixed liquid was prepared. Then, with stirring and emulsifying the monomer mixture, it was added to a reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 3.5 hours, and reacted until the polymerization conversion rate It reached 95%, and the aqueous dispersion of the particulate-form polymer 6 for negative electrodes was obtained. The minimum film forming temperature of the negative electrode particulate polymer 6 is 56°C, the glass transition temperature (Tg) is 50°C, and the primary particle diameter is 625nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物6的水分散体中除去水分,然后利用真空干燥机在40℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物6,得到了粉末状的负极用粘合剂6。粉末状的负极用粘合剂6的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 6 for negative electrodes at 40° C. by a rotary evaporator, and dried by a vacuum dryer at 40° C. and 0.6 kPa. Then, the dried particulate polymer 6 for negative electrodes was crushed with a mortar to obtain powdery binder 6 for negative electrodes. The 120° C. volatile content of the powdery negative electrode binder 6 was 0.1%.
除了使用了上述负极用粘合剂6之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 6 for negative electrodes was used.
<实施例7><Example 7>
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物1的水分散体中除去水分,然后,除了未利用真空干燥机在40℃、0.6kPa的条件下使其干燥之外,与实施例1同样地进行粒子状聚合物的干燥和破碎,得到了粉末状的负极用粘合剂7。粉末状的负极用粘合剂7的120℃挥发成分为0.8%。Use a rotary evaporator to remove water from the aqueous dispersion of the above-mentioned particulate polymer 1 for negative electrodes at 40°C, and then dry it at 40°C and 0.6kPa without using a vacuum dryer. 1. The particulate polymer was dried and crushed in the same manner to obtain a powdery negative electrode binder 7. The 120° C. volatile component of the powdery negative electrode binder 7 was 0.8%.
除了使用了上述负极用粘合剂7之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 7 for negative electrodes was used.
<比较例1><Comparative example 1>
(负极用粒子状聚合物7的制造)(Manufacture of Particulate Polymer 7 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯70份、1,3-丁二烯27份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、离子交换水150份、作为链转移剂的叔十二烷基硫醇0.3份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物7的水分散体。负极用粒子状聚合物7的最低制膜温度为27℃,玻璃化转变温度(Tg)为30℃,初级粒径为130nm。Add 70 parts of styrene, 27 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Company) 0.4 parts in terms of solid content equivalents, 150 parts of ion-exchanged water, 0.3 parts of tertiary dodecyl mercaptan as a chain transfer agent, and 0.5 parts of potassium persulfate as a polymerization initiator, fully stirred Then, it was heated to 75° C. to initiate polymerization. When the polymerization conversion ratio reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the particulate polymer 7 for negative electrodes was obtained. The minimum film-forming temperature of the negative electrode particulate polymer 7 was 27° C., the glass transition temperature (Tg) was 30° C., and the primary particle diameter was 130 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于20℃从上述负极用粒子状聚合物7的水分散体中除去水分,然后利用真空干燥机在20℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物7,得到了凝聚性稍高的粉末状的负极用粘合剂8。粉末状的负极用粘合剂8的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 7 for negative electrodes at 20° C. with a rotary evaporator, and then dried with a vacuum dryer at 20° C. and 0.6 kPa. Then, the dried particulate polymer 7 for negative electrodes was pulverized with a mortar to obtain a powdery binder 8 for negative electrodes with slightly high cohesiveness. The 120° C. volatile component of the powdery negative electrode binder 8 was 0.1%.
除了使用了上述负极用粘合剂8之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 8 for negative electrodes was used.
<比较例2><Comparative example 2>
(负极用粒子状聚合物8的制造)(Manufacture of Particulate Polymer 8 for Negative Electrodes)
向带搅拌机的5MPa耐压容器中加入苯乙烯94份、1,3-丁二烯3份、衣康酸3份、作为乳化剂的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、离子交换水150份以及作为聚合引发剂的过硫酸钾0.5份,进行充分的搅拌后,加温至75℃以引发聚合。在聚合转化率达到96%的时刻进行冷却,停止反应,得到了负极用粒子状聚合物8的水分散体。负极用粒子状聚合物8的最低制膜温度为120℃,玻璃化转变温度(Tg)为100℃,初级粒径为135nm。Add 94 parts of styrene, 3 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) 0.4 parts in terms of solid content equivalent, 150 parts of ion-exchanged water, and 0.5 parts of potassium persulfate as a polymerization initiator were sufficiently stirred, and then heated to 75° C. to initiate polymerization. When the polymerization conversion ratio reached 96%, cooling was performed to stop the reaction, and an aqueous dispersion of the particulate polymer 8 for negative electrodes was obtained. The minimum film forming temperature of the negative electrode particulate polymer 8 is 120°C, the glass transition temperature (Tg) is 100°C, and the primary particle diameter is 135nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于80℃从上述负极用粒子状聚合物8的水分散体中除去水分,然后利用真空干燥机在80℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物8,得到了粉末状的负极用粘合剂9。Moisture was removed from the aqueous dispersion of the particulate polymer 8 for negative electrodes at 80° C. by a rotary evaporator, and dried by a vacuum dryer at 80° C. and 0.6 kPa. Then, the dried particulate polymer 8 for negative electrodes was crushed with a mortar to obtain a powdery binder 9 for negative electrodes.
除了使用了上述负极用粘合剂9之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 9 for negative electrodes was used.
<比较例3><Comparative example 3>
(负极用粒子状聚合物9的制造)(Manufacture of Particulate Polymer 9 for Negative Electrodes)
相对于负极用粒子状聚合物1的水分散体,以相对于聚合物重量10份为100份的重量比添加甲苯,利用乳化分散装置(MilderMDN303V;太平洋机工公司制)以15000rpm进行了乳化。然后,使用旋转蒸发仪从该乳化液中除去溶剂,得到了负极用粒子状聚合物9的水分散体。负极用粒子状聚合物9的最低制膜温度为53℃,玻璃化转变温度(Tg)为50℃,初级粒径为3020nm。Toluene was added in a weight ratio of 10 parts to 100 parts by weight of the polymer to the aqueous dispersion of the particulate polymer 1 for negative electrodes, and was emulsified at 15000 rpm with an emulsification disperser (MilderMDN303V; manufactured by Pacific Machinery Co., Ltd.). Then, the solvent was removed from this emulsion using a rotary evaporator to obtain an aqueous dispersion of particulate polymer 9 for negative electrodes. The minimum film forming temperature of the negative electrode particulate polymer 9 was 53°C, the glass transition temperature (Tg) was 50°C, and the primary particle diameter was 3020 nm.
(粒子状聚合物的干燥和破碎)(drying and crushing of granular polymers)
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物9的水分散体中除去水分,然后利用真空干燥机在40℃、0.6kPa的条件下使其干燥。然后,利用研钵破碎经干燥的负极用粒子状聚合物9,得到了粉末状的负极用粘合剂10。粉末状的负极用粘合剂10的120℃挥发成分为0.1%。Moisture was removed from the aqueous dispersion of the particulate polymer 9 for negative electrodes at 40° C. by a rotary evaporator, and then dried by a vacuum dryer at 40° C. and 0.6 kPa. Then, the dried particulate polymer 9 for negative electrodes was crushed with a mortar to obtain a powdery binder 10 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 10 was 0.1%.
除了使用了上述负极用粘合剂10之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 10 for negative electrodes was used.
<比较例4><Comparative example 4>
利用旋转蒸发仪于40℃从上述负极用粒子状聚合物1的水分散体中除去水分时,在中途停止水分的除去,得到了粉末状的负极用粘合剂11。粉末状的负极用粘合剂11的120℃挥发成分为2%。When water was removed from the aqueous dispersion of the particulate polymer 1 for negative electrodes by a rotary evaporator at 40° C., the removal of water was stopped halfway to obtain a powdery binder 11 for negative electrodes. The 120° C. volatile content of the powdery negative electrode binder 11 was 2%.
除了使用了上述负极用粘合剂11之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 1 except that the above-mentioned binder 11 for negative electrodes was used.
<比较例5><Comparative example 5>
利用旋转蒸发仪于60℃从上述负极用粒子状聚合物1的水分散体中除去水分,然后利用真空干燥机在60℃、0.6kPa的条件下使其干燥。然后,利用研钵粉碎经膜化了的负极用粒子状聚合物1,然后进一步利用喷射磨进行粉碎直到平均粒径达到5000nm左右,得到了粉末状的负极用粘合剂12。粉末状的负极用粘合剂12的120℃挥发成分为0.1%。Moisture content was removed from the aqueous dispersion of the particulate polymer 1 for negative electrodes at 60° C. by a rotary evaporator, and then dried by a vacuum dryer at 60° C. and 0.6 kPa. Then, the film-formed particulate polymer 1 for negative electrodes was pulverized with a mortar, and further pulverized with a jet mill until the average particle diameter reached about 5000 nm, thereby obtaining a powdery binder 12 for negative electrodes. The 120° C. volatile component of the powdery negative electrode binder 12 was 0.1%.
除了使用了上述负极用粘合剂12之外,与实施例1同样地进行了负极的制造及锂离子二次电池的制造。Production of a negative electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 1 except that the above-mentioned binder 12 for negative electrodes was used.
<实施例8><Embodiment 8>
(正极用粒子状聚合物1的制造)(Manufacture of Particulate Polymer 1 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中,进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯(以下也简称为“BA”)20份、甲基丙烯酸乙酯(以下也简称为“EMA”)77.5份、甲基丙烯酸(以下也简称为“MAA”)2.4份、甲基丙烯酸烯丙酯(以下也简称为“AMA”)0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计1.0份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物1(丙烯酸类聚合物;以下也简称为“丙烯酸类”)的水分散体。此外,正极用粒子状聚合物1的最低制膜温度为45℃,玻璃化转变温度(Tg)为40℃,初级粒径为310nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, 20 parts of butyl acrylate (hereinafter also referred to as "BA") and ethyl methacrylate (hereinafter also referred to as "BA") were added in a nitrogen atmosphere. EMA") 77.5 parts, methacrylic acid (hereinafter also referred to as "MAA") 2.4 parts, allyl methacrylate (hereinafter also referred to as "AMA") 0.1 part, alkyldimethacrylate with a concentration of 30% as an emulsifier 1.0 parts of phenylene ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) and 22.7 parts of ion-exchanged water were stirred and emulsified by solid content equivalent, and a monomer mixed liquid was prepared. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and an aqueous dispersion of the positive electrode particulate polymer 1 (acrylic polymer; hereinafter also simply referred to as "acrylic") was obtained. In addition, the minimum film forming temperature of the particulate polymer 1 for positive electrodes was 45° C., the glass transition temperature (Tg) was 40° C., and the primary particle diameter was 310 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物1的水分散体进行喷雾干燥造粒,并利用真空干燥机在30℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂1。粉末状的正极用粘合剂1的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 1 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 30° C. and 0.6 kPa to obtain a powdery positive electrode binder 1 . The 120° C. volatile component of the powdery positive electrode binder 1 was 0.1%.
(粒子复合体的制造)(Manufacture of particle complexes)
对于作为正极活性物质的NMC(111)92.5份、作为导电剂的乙炔黑6份以及上述正极用粘合剂以固体成分换算量计1.5份,使用亨舍尔混合机(三井三池公司制)混合10分钟,使正极用粘合剂附着于正极活性物质,得到了粒子复合体。For 92.5 parts of NMC (111) as a positive electrode active material, 6 parts of acetylene black as a conductive agent, and 1.5 parts of the above-mentioned positive electrode binder in terms of solid content, they were mixed using a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) After 10 minutes, the positive electrode binder was adhered to the positive electrode active material to obtain a particle composite.
(正极的制造)(production of positive electrode)
使用定量给料机(Nikka公司制“NikkasprayK-V”)将上述得到的粒子复合体供给至辊压机(HIRANOGIKENKOGYO公司制“剪切粗面热辊”)的压制用辊(辊温度100℃、压制线压500kN/m)。在压制用辊间插入厚度20μm的铝箔,使从定量给料机供给的上述粒子复合体附着在铝箔上,以成型速度1.5m/分钟进行加压成型,得到了具有正极活性物质的正极。The particle composite obtained above was supplied to the pressing roll (roll temperature 100° C., 100° C., Compression line pressure 500kN/m). An aluminum foil with a thickness of 20 μm was inserted between pressing rolls, and the particle composite supplied from a quantitative feeder was attached to the aluminum foil, and press-molded at a molding speed of 1.5 m/min to obtain a positive electrode having a positive electrode active material.
(负极用浆料以及负极的制造)(Manufacture of negative electrode slurry and negative electrode)
将作为负极活性物质的人造石墨(平均粒径:24.5μm、石墨层间距(基于X射线衍射法测定的(002)面的面间隔(d值)):0.354nm)96份、苯乙烯-丁二烯共聚胶乳(BM-400B)以固体成分换算量计3.0份、羧甲基纤维素的1.5%水溶液(DN-800H:Daicel化学工业公司制)以固体成分换算量1.0份混合,然后添加离子交换水使得固体成分浓度达到50%,进行混合分散,得到了负极用浆料。将该负极用浆料涂布至厚度18μm的铜箔、于120℃干燥30分钟,然后进行辊压,得到了厚度50μm的负极。As a negative electrode active material, 96 parts of artificial graphite (average particle size: 24.5 μm, distance between graphite layers (interplanar distance (d value) of (002) plane measured by X-ray diffraction method): 0.354 nm), styrene-butadiene 3.0 parts of diene copolymer latex (BM-400B) in terms of solid content and 1.0 parts of carboxymethylcellulose in an aqueous solution (DN-800H: Daicel Chemical Industry Co., Ltd.) 1.0 parts in terms of solid content were mixed, and then ions were added. Water was exchanged so that the solid content concentration became 50%, and the mixture was mixed and dispersed to obtain a negative electrode slurry. This negative electrode slurry was applied to a copper foil with a thickness of 18 μm, dried at 120° C. for 30 minutes, and then rolled to obtain a negative electrode with a thickness of 50 μm.
(隔板的准备)(Preparation of partitions)
将单层的聚丙烯制隔板(宽65mm、长500mm、厚25μm,利用干式法制造,气孔率55%)冲切为5×5cm2的正方形。A single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 μm, manufactured by a dry method, porosity 55%) was punched out into a square of 5×5 cm 2 .
(锂离子二次电池的制造)(manufacture of lithium-ion secondary batteries)
作为电池的外包装,准备了铝外包装材料。将上述得到的正极冲切为4×4cm2的正方形,以使集电体侧的表面与铝外包装材料接触的方式进行了配置。另外,在上述得到的正极的正极活性物质层的面上配置了上述得到的正方形的隔板。然后,将上述得到的负极切成4.2×4.2cm2的正方形,以使负极活性物质层侧的表面面向隔板的方式配置在隔板上。进一步,填充了含有2.0%的碳酸亚乙烯酯的、浓度为1.0M的LiPF6溶液。该LiPF6溶液的溶剂为碳酸亚乙酯(EC)和碳酸甲乙酯(EMC)的混合溶剂(EC/EMC=3/7(体积比))。进而,为了将铝包装材料的开口密封,于150℃进行热封而将铝外包装封口,制造了层压型的锂离子二次电池(层压型电池)。As the outer packaging of the battery, an aluminum outer packaging material was prepared. The positive electrode obtained above was punched out into a square of 4×4 cm 2 , and arranged so that the surface on the collector side was in contact with the aluminum exterior material. Moreover, the square separator obtained above was arrange|positioned on the surface of the positive electrode active material layer of the positive electrode obtained above. Then, the negative electrode obtained above was cut into a square of 4.2×4.2 cm 2 , and placed on the separator so that the surface on the side of the negative electrode active material layer faced the separator. Further, a LiPF 6 solution having a concentration of 1.0 M containing 2.0% of vinylene carbonate was filled. The solvent of the LiPF 6 solution is a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (EC/EMC=3/7 (volume ratio)). Furthermore, in order to seal the opening of the aluminum packaging material, heat sealing was performed at 150 degreeC, and the aluminum outer package was sealed, and the laminated type lithium ion secondary battery (laminated type battery) was manufactured.
<实施例9><Example 9>
(正极用粒子状聚合物2的制造)(Manufacture of Particulate Polymer 2 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯12份、甲基丙烯酸乙酯85.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计1.0份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物2的水分散体。此外,正极用粒子状聚合物2的最低制膜温度为52℃,玻璃化转变温度(Tg)为50℃,初级粒径为319nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, 12 parts of butyl acrylate, 85.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, and allyl methacrylate were added in a nitrogen atmosphere. 0.1 part, 1.0 parts of solid content equivalent of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier, and 22.7 parts of ion-exchanged water were subjected to Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and an aqueous dispersion of the particulate polymer 2 for positive electrodes was obtained. In addition, the minimum film forming temperature of the particulate polymer 2 for positive electrodes was 52° C., the glass transition temperature (Tg) was 50° C., and the primary particle diameter was 319 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物2的水分散体进行喷雾干燥造粒,并利用真空干燥机在40℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂2。粉末状的正极用粘合剂2的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 2 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 40° C. and 0.6 kPa to obtain a powdery positive electrode binder 2 . The 120° C. volatile component of the powdery positive electrode binder 2 was 0.1%.
除了使用了上述正极用粘合剂2之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 8 except that the above-mentioned binder 2 for positive electrodes was used.
<实施例10><Example 10>
(正极用粒子状聚合物3的制造)(Manufacture of Particulate Polymer 3 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯6份、甲基丙烯酸乙酯91.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计1.0份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物3的水分散体。此外,正极用粒子状聚合物3的最低制膜温度为65℃,玻璃化转变温度(Tg)为60℃,初级粒径为331nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, 6 parts of butyl acrylate, 91.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, and allyl methacrylate were added in a nitrogen atmosphere. 0.1 part, 1.0 parts of solid content equivalent of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier, and 22.7 parts of ion-exchanged water were subjected to Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and the aqueous dispersion of the particulate polymer 3 for positive electrodes was obtained. In addition, the minimum film forming temperature of the particulate polymer 3 for positive electrodes was 65° C., the glass transition temperature (Tg) was 60° C., and the primary particle diameter was 331 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物3的水分散体进行喷雾干燥造粒,并利用真空干燥机在40℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂3。粉末状的正极用粘合剂3的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 3 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 40° C. and 0.6 kPa to obtain a powdery positive electrode binder 3 . The 120° C. volatile component of the powdery positive electrode binder 3 was 0.1%.
除了使用了上述正极用粘合剂3之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 3 for positive electrodes was used.
<实施例11><Example 11>
(正极用粒子状聚合物4的制造)(Manufacture of Particulate Polymer 4 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.5份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯20份、甲基丙烯酸乙酯77.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.5份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物4的水分散体。此外,正极用粒子状聚合物4的最低制膜温度为43℃,玻璃化转变温度(Tg)为40℃,初级粒径为139nm。In the reactor that mechanical stirrer and condenser are installed, feed ion-exchanged water 210 parts, the alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1 , DOW Chemical Co., Ltd.) 0.5 parts by solid content equivalent, it heated to 70 degreeC, stirring, and added 25.5 parts of 1.96% potassium persulfate aqueous solutions to a reactor. Then, in a different container from the above equipped with a mechanical stirrer, 20 parts of butyl acrylate, 77.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, and allyl methacrylate were added in a nitrogen atmosphere. 0.1 part, 0.5 part of solid content equivalent of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier, and 22.7 parts of ion-exchanged water were carried out. Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and an aqueous dispersion of the particulate polymer 4 for positive electrodes was obtained. In addition, the minimum film-forming temperature of the particulate polymer 4 for positive electrodes was 43° C., the glass transition temperature (Tg) was 40° C., and the primary particle diameter was 139 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物4的水分散体进行喷雾干燥造粒,并利用真空干燥机在30℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂4。粉末状的正极用粘合剂4的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65mm), set the rotation speed at 25,000rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 4 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 30° C. and 0.6 kPa to obtain a powdery positive electrode binder 4 . The 120° C. volatile component of the powdery positive electrode binder 4 was 0.1%.
除了使用了上述正极用粘合剂4之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 4 for positive electrodes was used.
<实施例12><Example 12>
(正极用粒子状聚合物5的制造)(Manufacture of Particulate Polymer 5 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.8份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯20份、甲基丙烯酸乙酯77.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.8份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物5的水分散体。此外,正极用粒子状聚合物5的最低制膜温度为43℃,玻璃化转变温度(Tg)为40℃,初级粒径为100nm。In the reactor that mechanical stirrer and condenser are installed, feed ion-exchanged water 210 parts, the alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1 , DOW Chemical Co., Ltd.) 0.8 parts by solid content equivalent, it heated to 70 degreeC, stirring, and added 25.5 parts of 1.96% potassium persulfate aqueous solutions to a reactor. Then, in a different container from the above equipped with a mechanical stirrer, 20 parts of butyl acrylate, 77.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, and allyl methacrylate were added in a nitrogen atmosphere. 0.1 part, 0.8 parts of solid content equivalent of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier, and 22.7 parts of ion-exchanged water were subjected to Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and an aqueous dispersion of the particulate polymer 5 for positive electrodes was obtained. In addition, the minimum film-forming temperature of the positive electrode particulate polymer 5 was 43° C., the glass transition temperature (Tg) was 40° C., and the primary particle diameter was 100 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物5的水分散体进行喷雾干燥造粒,并利用真空干燥机在30℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂5。粉末状的正极用粘合剂5的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotating disc sprayer (diameter 65mm), set the rotation speed at 25,000rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 5 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 30° C. and 0.6 kPa to obtain a powdery positive electrode binder 5 . The 120° C. volatile component of the powdery positive electrode binder 5 was 0.1%.
除了使用了上述正极用粘合剂5之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 5 for positive electrodes was used.
<实施例13><Example 13>
(正极用粒子状聚合物6的制造)(Manufacture of Particulate Polymer 6 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯20份、甲基丙烯酸乙酯77.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计0.4份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物6的水分散体。此外,正极用粒子状聚合物6的最低制膜温度为48℃,玻璃化转变温度(Tg)为40℃,初级粒径为625nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, 20 parts of butyl acrylate, 77.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, and allyl methacrylate were added in a nitrogen atmosphere. 0.1 part, as an emulsifier, 0.4 parts of an alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% in terms of solid content equivalents, and 22.7 parts of ion-exchanged water were subjected to Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion ratio reached 95%, and an aqueous dispersion of the particulate polymer 6 for positive electrodes was obtained. In addition, the minimum film forming temperature of the particulate polymer 6 for positive electrodes was 48° C., the glass transition temperature (Tg) was 40° C., and the primary particle diameter was 625 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物6的水分散体进行喷雾干燥造粒,并利用真空干燥机在30℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂6。粉末状的正极用粘合剂6的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65mm), set the rotation speed at 25,000rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 6 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 30° C. and 0.6 kPa to obtain a powdery positive electrode binder 6 . The 120° C. volatile component of the powdery positive electrode binder 6 was 0.1%.
除了使用了上述正极用粘合剂6之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 8 except that the above-mentioned binder 6 for positive electrodes was used.
<实施例14><Example 14>
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物1的水分散体进行喷雾干燥造粒,得到了粒子。然后,除了未利用真空干燥机在30℃、0.6kPa的条件下使得到的粒子干燥之外,与实施例8同样地进行粒子状聚合物的干燥,得到了粉末状的正极用粘合剂7。粉末状的正极用粘合剂7的120℃挥发成分为0.8%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 1 in water. The body was spray-dried and granulated to obtain particles. Then, except that the obtained particles were not dried under the conditions of 30° C. and 0.6 kPa using a vacuum dryer, the particulate polymer was dried in the same manner as in Example 8 to obtain a powdery positive electrode binder 7 . The 120° C. volatile component of the powdery positive electrode binder 7 was 0.8%.
除了使用了上述正极用粘合剂7之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 7 for a positive electrode was used.
<比较例6><Comparative example 6>
(正极用粒子状聚合物7的制造)(Manufacture of Particulate Polymer 7 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加丙烯酸丁酯27.6份、甲基丙烯酸乙酯70.0份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计1.0份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物7的水分散体。此外,正极用粒子状聚合物7的最低制膜温度为27℃,玻璃化转变温度(Tg)为30℃,初级粒径为307nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, in a nitrogen atmosphere, 27.6 parts of butyl acrylate, 70.0 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, allyl methacrylate 0.1 part, 1.0 parts of solid content equivalent of alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier, and 22.7 parts of ion-exchanged water were subjected to Stir and emulsify to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion ratio reached 95%, and an aqueous dispersion of the particulate polymer 7 for positive electrodes was obtained. In addition, the minimum film-forming temperature of the positive electrode particulate polymer 7 was 27° C., the glass transition temperature (Tg) was 30° C., and the primary particle diameter was 307 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物7的水分散体进行喷雾干燥造粒,并利用真空干燥机在25℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂8。粉末状的正极用粘合剂8的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 7 in water The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 25° C. and 0.6 kPa to obtain powdery positive electrode binder 8 . The 120° C. volatile component of the powdery positive electrode binder 8 was 0.1%.
除了使用了上述正极用粘合剂8之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 8 for positive electrodes was used.
<比较例7><Comparative example 7>
(正极用粒子状聚合物8的制造)(Manufacture of Particulate Polymer 8 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中进料离子交换水210份,边搅拌边加热至70℃,并将1.96%过硫酸钾水溶液25.5份添加至反应器。然后,向安装有机械搅拌器的与上述不同的另外的容器中,在氮气氛围中,添加甲基丙烯酸乙酯22.5份、甲基丙烯酸甲酯(以下也简称为“MMA”)75.0份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份、作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计1.0份、及离子交换水22.7份,对其进行搅拌乳化,从而制备了单体混合液。然后,在使该单体混合液搅拌乳化的状态下,经2.5小时以恒定速度,将该单体混合液添加至已进料有离子交换水210份及过硫酸钾水溶液的反应器,使其反应直到聚合转化率达到95%,得到了正极用粒子状聚合物8的水分散体。此外,正极用粒子状聚合物8的最低制膜温度为115℃,玻璃化转变温度(Tg)为100℃,初级粒径为280nm。Into a reactor equipped with a mechanical stirrer and a condenser, 210 parts of ion-exchanged water was fed in a nitrogen atmosphere, heated to 70°C while stirring, and 25.5 parts of 1.96% potassium persulfate aqueous solution was added to the reactor. Then, in a different container from the above equipped with a mechanical stirrer, 22.5 parts of ethyl methacrylate, 75.0 parts of methyl methacrylate (hereinafter also abbreviated as "MMA"), and methyl methacrylate were added in a nitrogen atmosphere. 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate, 1.0 parts of a solid content equivalent of an alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, manufactured by DOW Chemical Co., Ltd.) with a concentration of 30% as an emulsifier , and 22.7 parts of ion-exchanged water were stirred and emulsified to prepare a monomer mixture. Then, in the state where the monomer mixed solution was stirred and emulsified, the monomer mixed solution was added to the reactor fed with 210 parts of ion-exchanged water and an aqueous potassium persulfate solution at a constant speed for 2.5 hours to make it The reaction was carried out until the polymerization conversion rate reached 95%, and an aqueous dispersion of the particulate polymer 8 for positive electrodes was obtained. In addition, the minimum film forming temperature of the particulate polymer 8 for positive electrodes was 115° C., the glass transition temperature (Tg) was 100° C., and the primary particle diameter was 280 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物8的水分散体进行喷雾干燥造粒,并利用真空干燥机在80℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂9。粉末状的正极用粘合剂9的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65mm), set the rotation speed at 25,000rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 8 in water. The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 80° C. and 0.6 kPa to obtain a powdery positive electrode binder 9 . The 120° C. volatile component of the powdery positive electrode binder 9 was 0.1%.
除了使用了上述正极用粘合剂9之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were carried out in the same manner as in Example 8 except that the above-mentioned binder 9 for positive electrodes was used.
<比较例8><Comparative example 8>
(正极用粒子状聚合物9的制造)(Manufacture of Particulate Polymer 9 for Positive Electrodes)
向安装有机械搅拌器及冷凝器的反应器中,在氮气氛围中添加离子交换水831份和作为乳化剂的浓度30%的烷基二苯醚二磺酸盐(DOWFAX(注册商标)2A1、DOWChemical公司制)以固体成分当量计10份,并添加丙烯酸丁酯6份、甲基丙烯酸乙酯91.5份、甲基丙烯酸2.4份、甲基丙烯酸烯丙酯0.1份,对该单体混合液进行搅拌乳化。边对其进行搅拌边加热至60℃,将1.96%过硫酸钾水溶液51份添加至反应器。进行反应直到聚合转化率达到98%,得到了正极用粒子状聚合物9的水分散体。此外,正极用粒子状聚合物9的最低制膜温度为42℃,玻璃化转变温度(Tg)为60℃,初级粒径为50nm。In a reactor equipped with a mechanical stirrer and a condenser, 831 parts of ion-exchanged water and 30% alkyl diphenyl ether disulfonate (DOWFAX (registered trademark) 2A1, DOWFAX (registered trademark) 2A1, DOW Chemical Co., Ltd.) 10 parts in terms of solid content equivalent, 6 parts of butyl acrylate, 91.5 parts of ethyl methacrylate, 2.4 parts of methacrylic acid, 0.1 part of allyl methacrylate were added, and the monomer mixture was Stir to emulsify. It heated to 60 degreeC, stirring this, and added 51 parts of 1.96% potassium persulfate aqueous solutions to a reactor. The reaction was carried out until the polymerization conversion rate reached 98%, and an aqueous dispersion of the particulate polymer 9 for positive electrodes was obtained. In addition, the minimum film-forming temperature of the positive electrode particulate polymer 9 was 42° C., the glass transition temperature (Tg) was 60° C., and the primary particle diameter was 50 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物9的水分散体进行喷雾干燥造粒,并利用真空干燥机在40℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂10。粉末状的正极用粘合剂10的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40° C. to disperse the above-mentioned positive electrode particulate polymer 9 in water The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 40° C. and 0.6 kPa to obtain a powdery positive electrode binder 10 . The 120° C. volatile component of the powdery positive electrode binder 10 was 0.1%.
除了使用了上述正极用粘合剂10之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 8 except that the above-mentioned binder 10 for positive electrodes was used.
<比较例9><Comparative example 9>
(正极用粒子状聚合物10的制造)(Manufacture of Particulate Polymer 10 for Positive Electrodes)
相对于正极用粒子状聚合物1的水分散体,以相对于聚合物重量10份为100份的重量比添加甲苯,利用乳化分散装置(MilderMDN303V;太平洋机工公司制)以15000rpm进行了乳化。然后,使用旋转蒸发仪从该乳化液中除去溶剂,得到了正极用粒子状聚合物10的水分散体。正极用粒子状聚合物10的最低制膜温度为53℃,玻璃化转变温度(Tg)为40℃,初级粒径为3050nm。Toluene was added in a weight ratio of 100 parts to the weight of the polymer to the aqueous dispersion of the particulate polymer 1 for positive electrodes, and emulsified at 15000 rpm with an emulsification disperser (MilderMDN303V; manufactured by Pacific Machinery Co., Ltd.). Then, the solvent was removed from this emulsion liquid using a rotary evaporator, and the aqueous dispersion of the particulate-form polymer 10 for positive electrodes was obtained. The minimum film forming temperature of the particulate polymer 10 for positive electrodes was 53° C., the glass transition temperature (Tg) was 40° C., and the primary particle diameter was 3050 nm.
(粒子状聚合物的干燥)(drying of particulate polymer)
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物9的水分散体进行喷雾干燥造粒,并利用真空干燥机在40℃、0.6kPa的条件下,使得到的粒子干燥,得到了粉末状的正极用粘合剂11。粉末状的正极用粘合剂11的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40° C. to disperse the above-mentioned positive electrode particulate polymer 9 in water The body was spray-dried and granulated, and the obtained particles were dried using a vacuum dryer under the conditions of 40° C. and 0.6 kPa to obtain a powdery positive electrode binder 11 . The 120° C. volatile component of the powdery positive electrode binder 11 was 0.1%.
除了使用了上述正极用粘合剂11之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 8 except that the above-mentioned binder 11 for positive electrodes was used.
<比较例10><Comparative Example 10>
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为30℃,对上述正极用粒子状聚合物1的水分散体进行喷雾干燥造粒,未对所得粒子进行真空干燥,得到了粉末状的正极用粘合剂12。粉末状的正极用粘合剂12的120℃挥发成分为2%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 30°C to disperse the above-mentioned positive electrode particulate polymer 1 in water. The body was spray-dried and granulated, and the obtained particles were not vacuum-dried to obtain a powdery positive electrode binder 12 . The 120° C. volatile content of the powdery positive electrode binder 12 was 2%.
除了使用了上述正极用粘合剂12之外,与实施例8同样地进行了正极的制造及锂离子二次电池的制造。Production of a positive electrode and production of a lithium ion secondary battery were performed in the same manner as in Example 8 except that the above-mentioned binder 12 for positive electrodes was used.
<比较例11><Comparative Example 11>
在喷雾干燥机(大川原化工机公司制)中,使用旋转圆盘方式的喷雾器(直径65mm),设定转速为25,000rpm、热风温度为40℃,对上述正极用粒子状聚合物1的水分散体进行喷雾干燥造粒,并利用真空干燥机在70℃、0.6kPa的条件下,使得到的粒子干燥。然后,利用研钵粉碎经膜化了的正极用粒子状聚合物1,然后进一步利用喷射磨进行粉碎直到平均粒径达到5000nm左右,得到了粉末状的正极用粘合剂13。粉末状的正极用粘合剂13的120℃挥发成分为0.1%。In a spray dryer (manufactured by Okawara Chemical Machinery Co., Ltd.), using a rotary disc sprayer (diameter 65 mm), set the rotation speed at 25,000 rpm, and the hot air temperature at 40°C to disperse the above-mentioned positive electrode particulate polymer 1 in water. The body was spray-dried and granulated, and the obtained particles were dried under the conditions of 70° C. and 0.6 kPa using a vacuum dryer. Then, the membrane-formed particulate polymer 1 for positive electrodes was pulverized with a mortar, and further pulverized with a jet mill until the average particle diameter reached about 5000 nm, thereby obtaining a powdery binder 13 for positive electrodes. The 120° C. volatile component of the powdery positive electrode binder 13 was 0.1%.
如表1及表2所示的那样,使用包含下述电极用粘合剂的粒子复合体而制造的电极的电极精度、柔软性良好,进而,使用该电极的锂离子二次电池的速率特性良好,所述电极用粘合剂由玻璃化转变温度为35~80℃、初级粒子的体积基准D50平均粒径为80~1000nm的聚合物形成,其在120℃时的挥发成分少于1重量%,且该粘合剂为粉末状复合化粒子。As shown in Table 1 and Table 2, the electrode accuracy and flexibility of the electrode manufactured using the particle composite comprising the following electrode binder are good, and the rate characteristics of the lithium ion secondary battery using the electrode Good, the electrode binder is formed of a polymer with a glass transition temperature of 35 to 80°C and an average particle diameter of 80 to 1000 nm on a volume basis D50 of primary particles, and its volatile component at 120°C is less than 1 wt. %, and the binder is a powdery composite particle.
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