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WO2020107927A1 - 天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用 - Google Patents

天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用 Download PDF

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Publication number
WO2020107927A1
WO2020107927A1 PCT/CN2019/098885 CN2019098885W WO2020107927A1 WO 2020107927 A1 WO2020107927 A1 WO 2020107927A1 CN 2019098885 W CN2019098885 W CN 2019098885W WO 2020107927 A1 WO2020107927 A1 WO 2020107927A1
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Prior art keywords
natural graphite
preparation
optionally
treatment
modified natural
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PCT/CN2019/098885
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English (en)
French (fr)
Inventor
李东东
周海辉
周成坤
吴璇
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贝特瑞新材料集团股份有限公司
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Application filed by 贝特瑞新材料集团股份有限公司 filed Critical 贝特瑞新材料集团股份有限公司
Priority to EP19890538.2A priority Critical patent/EP3780181A4/en
Priority to JP2020569793A priority patent/JP7119131B2/ja
Priority to KR1020207032516A priority patent/KR20200139817A/ko
Priority to US17/043,350 priority patent/US20210017028A1/en
Publication of WO2020107927A1 publication Critical patent/WO2020107927A1/zh

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    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Definitions

  • the present application belongs to the technical field of negative electrode materials, and relates to a natural graphite and a modified natural graphite material prepared therefrom, a preparation method and an application.
  • the battery cell of a power lithium-ion battery is mainly composed of a negative electrode, an electrolyte, a separator, and a positive electrode.
  • the positive and negative electrodes have a decisive influence on the performance of the battery. Therefore, the focus of power battery research and development is to develop low-cost and excellent electrode materials.
  • the negative electrode material graphite material is still in a dominant position. Graphite can be subdivided into artificial and natural graphite according to the source. Artificial graphite needs to undergo an ultra-high temperature graphitization process, making its price difficult to drop. Natural graphite does not require a high-temperature graphitization process, so it has obvious cost advantages and occupies the main position in the negative electrode material market in the field of 3C.
  • CN107195903A discloses a small-diameter natural graphite anode material for lithium-ion power batteries and a preparation method thereof.
  • the invention adds a "two" between the finished product discharge port and the tail material discharge of the 15-25 ⁇ m natural graphite crushing equipment. Feed port", to collect graphite materials with a particle size range of 5-25 ⁇ m and a tap density greater than 0.65 g/cm 3 , and then undergo new shaping, chemical purification, and asphalt-coated carbonization to obtain small-diameter high-capacity natural graphite anode materials, but their For the first time, Coulomb efficiency and rate performance are still poor.
  • CN106629702A discloses a processing method of high-cycle natural graphite negative electrode material, which adopts the following preparation steps: (1) Mixing: the natural graphite raw material and the modifier are uniformly mixed at a mass ratio of 100:0 to 30 to obtain a mixture; (2) Isostatic treatment; (3) crushing; (4) surface modification; (5) cooling classification.
  • the natural graphite is densified and modified.
  • the modifier enters into the material under the action of external pressure to fill the voids. After heat treatment, the modifier forms a stable structure of amorphous carbon or artificial graphite.
  • CN106744916A discloses a method for modifying a negative electrode material of a high-rate lithium ion battery, which includes the following processing steps: (1) Raw material mixing: resin powder and graphite raw material are uniformly mixed at a weight ratio of 1:100 to 15:100; (2 ) Medium temperature carbonization treatment: In an inert atmosphere, heat up to 600 ⁇ 1300 °C, and maintain a constant temperature at this temperature for 1 ⁇ 4h; (3) After cooling, classification treatment to obtain modified lithium ion battery graphite anode material.
  • the invention adopts a specific resin to coat and modify graphite particles to prepare a negative electrode material of a lithium ion battery.
  • the composite material prepared by this method has poor rate performance and first-time Coulomb efficiency.
  • the purpose of this application is to provide a natural graphite and the modified natural graphite material prepared from it, its preparation method and application.
  • the present application provides a natural graphite having the following characteristics:
  • This application provides a kind of natural graphite with specific particle size, specific orientation, specific tap density and specific surface area.
  • the modified natural graphite material prepared from specific selected natural graphite will have higher isotropy Excellent rate performance and cycle performance.
  • the particle size of the present application is obtained by testing with a particle size tester, and information such as the 002 plane spacing is obtained by XRD test, and its specific surface area is obtained by nitrogen adsorption and desorption test.
  • the limitation of natural graphite is indispensable. Only by selecting the above-defined natural graphite can a modified natural graphite material with excellent properties be prepared. When the average particle size and particle size distribution of natural graphite are not within the limits of this application, it will cause unsatisfactory solidification effect during processing, and the particle size distribution (D90/D10) is too large, which will reduce the modified natural graphite material.
  • the particle size D50 ⁇ 10 ⁇ m such as 9 ⁇ m, 8.5 ⁇ m, 8 ⁇ m, 7 ⁇ m, 6 ⁇ m, 4 ⁇ m, etc., and D90/D10 ⁇ 2.5, such as 2.47, 2.45, 2.4, 2.38, 2.35, 2.2, 2.0, 1.8, 1.5, etc.
  • the I 002 /I 110 ⁇ 35 for example, 34, 33.5, 33.2, 33, 32.4, 32, 30, etc.
  • the natural graphite is obtained by crushing natural flake graphite or by crushing and shaping microcrystalline graphite.
  • the natural graphite provided in this application may be natural flake graphite for screening, or may be prepared by a preparation method.
  • the present application provides a modified natural graphite material.
  • the raw material for preparing the modified natural graphite material includes the natural graphite described in the first aspect.
  • the present application provides the method for preparing the modified natural graphite material according to the second aspect.
  • the preparation method is to modify the natural graphite to obtain the modified natural graphite material;
  • the modification treatment includes: sequentially solidifying, isotropically treating, carbonizing, and crushing the natural graphite.
  • the natural graphite with the above characteristics is first bonded and solidified, and then can be treated with an isotropic process to further improve the isotropy of natural graphite.
  • the treatment method of this application is more effective Obtained modified natural graphite with high isotropy degree.
  • the solidifying agent for solidification has a softening point of 20-300°C (eg, 40°C, 50°C, 60°C, 80°C, 100°C, 120°C, 150°C, 180°C, 200°C, 220 °C, 250 °C, 280 °C, etc.) phenolic resin, epoxy resin, petroleum resin, coal pitch, petroleum pitch, mesophase pitch, coal tar or heavy oil or any combination of at least two.
  • the mass ratio of the natural graphite to the solidifying agent is 1: (0.05-1), for example, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6 , 1:0.7, 1:0.8, 1:0.9, etc.
  • the solidification is performed under heating and stirring.
  • the heating temperature is 50-800°C, such as 100°C, 200°C, 400°C, 500°C, 600°C, 700°C, etc.
  • the stirring time is 0-300 min, such as 1 min, 5 min, 10 min, 50 min, 80 min, 120 min, 150 min, 180 min, 200 min, 220 min, 250 min, 280 min, etc.
  • the isotropic treatment includes any one or a combination of at least two of cold isostatic pressing treatment, hot isostatic pressing treatment, or molding treatment.
  • the temperature of the carbonization treatment is 1000-3000°C, for example, 1200°C, 1500°C, 1800°C, 2000°C, 2200°C, 2500°C, 2800°C, etc.
  • the carbonization treatment is performed under an inert gas environment.
  • the inert gas is any one or a combination of at least two of helium, neon, argon, nitrogen, or krypton.
  • the preparation method further includes sieving after crushing.
  • the particle size of the product after sieving is: 7 ⁇ m ⁇ D50 ⁇ 18 ⁇ m, such as 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, etc.
  • the modified natural graphite material of the present application has simple preparation process, easy operation, low cost and high practicability.
  • the present application provides a lithium ion battery including the modified natural graphite material described in the second aspect.
  • the negative pole piece of the lithium ion battery includes the modified natural graphite material described in the second aspect.
  • This application provides natural graphite with specific particle size, specific orientation, specific tap density and specific surface area, which is used as the preparation raw material, and the modified natural graphite material finally prepared has high isotropy, and Has better rate performance and cycle performance;
  • the modified natural graphite material obtained by the preparation method provided in this application has a 5C/1C discharge capacity retention rate at room temperature of more than 94%, and a 1C/1C charge and discharge 300 times capacity retention rate exceeds 90.2%.
  • a modified natural graphite material is as follows:
  • Mix at a ratio of 1:0.25 then put the mixed materials into a specific reactor for stirring and heating, the heating temperature is 360 °C, and keep for 3 hours, the heated materials are cold isostatically pressed, and the treatment pressure is 120MPa, time is 2min.
  • the product after isostatic pressing was subjected to carbonization treatment at 2800°C, after which the material was crushed to the approximate particle size of the raw material, and sieved to obtain a modified natural graphite material with a D50 of 8.3 ⁇ m.
  • Example 2 The difference from Example 1 is only that in this example, the mass ratio of natural graphite to coal pitch is 1:0.05 (Example 2), 1:1 (Example 3), 1:0.01 (Example 4 ), 1:2 (Example 5).
  • Example 2 The difference from Example 1 is only that in this example, the solidifying agent is a phenolic resin (softening point is 110°C).
  • the solidifying agent is a phenolic resin (softening point is 110°C).
  • Mix at a ratio of 1:0.3 then put the mixed materials into a specific reactor for stirring and heating, the heating temperature is 260 °C, and keep for 3 hours, the heated materials are cold isostatically pressed, and the treatment pressure is 110MPa, time is 1min.
  • the product after isostatic pressing was subjected to carbonization treatment at 2800°C, after which the material was crushed to the approximate particle size of the raw material, and sieved to obtain a modified natural graphite material with a D50 of 11.1 ⁇ m.
  • Mix at a ratio of 1:0.2 and then put the mixed materials into a specific reactor for stirring and heating, the heating temperature is 360 °C, and keep for 3 hours, the heated materials are cold isostatically pressed, and the treatment pressure is 80MPa, time is 1min.
  • the product after isostatic pressing was carbonized at 1200°C, and then the material was crushed to the approximate particle size of the raw material and sieved to obtain a modified natural graphite material with a D50 of 12.8 ⁇ m.
  • Example 1 The difference from Example 1 is only that in this comparative example, D50 of natural graphite is 15 ⁇ m.
  • Example 1 The difference from Example 1 is only that in this comparative example, the saturated tap density of natural graphite is 0.42 g/cc.
  • Example 1 The difference from Example 1 is only that in the present comparative example, the specific surface area of natural graphite is 12 m 2 /g.
  • Particle size use particle size tester to test
  • the modified natural graphite materials prepared in Examples 1-8 and Comparative Examples 1-5 were used as negative pole pieces and batteries as follows:
  • Battery mix the provided modified natural graphite material, conductive agent, CMC and SBR at a mass ratio of 95:1.5:1.5:2 and apply it to copper foil to obtain a negative pole piece; the positive electrode active material LiCoO 2 and the conductive agent ⁇ PVDF is evenly mixed according to the mass ratio of 96.5:2:1.5 and then coated on aluminum foil to obtain a positive pole piece; the electrolyte is 1mol/L LiPF 6 +EC+EMC, and the separator is a polyethylene/propylene composite microporous membrane.
  • the performance test of the prepared negative pole piece and battery is as follows:
  • the prepared negative electrode plate was tested for a button battery, the battery was assembled in an argon glove box, the metal lithium plate was used as the negative electrode, and the electrolyte was 1mol/L LiPF 6 + EC+EMC, the membrane is polyethylene/propylene composite microporous membrane, the electrochemical performance is carried out on the Xinwei battery test cabinet (5V, 1A), the charge and discharge voltage is 0.01-1.5V, the charge and discharge rate is 0.1C, test it Deduction capacity and first coulomb efficiency;
  • the test method of 5C/1C discharge capacity retention rate is: a. After the volume is divided, the battery is charged at 1C and discharged continuously for three times, and the average value of the three discharges is taken as the discharge capacity of 1C, and then the same battery is used for 1C charging, 5C discharge, continuous Perform 5 times, and take the average value of the last three discharges as 5C discharge capacity; 5C/1C discharge capacity retention rate is 5C discharge capacity divided by 1C discharge capacity;
  • the 1C/1C capacity retention rate test method is: 1C charging and 1C discharging are continuously charged and discharged for 300 weeks, with an interval of 1 minute after each charge and discharge is completed.
  • the modified natural graphite material provided in this application has a deduction capacity of more than 348mAh/g, a first coulombic efficiency of more than 90.2%, a discharge capacity retention rate of 5C/1C of more than 94%, and 1C/1C
  • the discharge capacity retention rate is above 91%. It can be known from the comparison between Examples 1-3 and Examples 4-5 that when the mass ratio of natural graphite and solidifying agent of the present application is 1: (0.05-1), the material finally obtained has better performance.
  • Example 1 Comparative Examples 1-5 that when the selected preparation raw material is not within the scope defined by this application, although the deduction capacity and the first coulomb efficiency are not much different, the modified natural graphite material obtained in this application Has better rate performance. Therefore, only the natural graphite defined in this application is selected and the modified natural graphite material prepared by the preparation method provided in this application has better performance.

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Abstract

一种天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用。所述天然石墨具有如下特征：(1)粒度D50<10μm，D90/D10<2.5；(2)002面间距为0.336-0.360，I 002/I 110≤35；(3)0.6g/cc≤饱和振实密度<1.3g/cc；(4)1.0m 2/g≤比表面积<10.0m 2/g。提供了具有特定粒度、特定取向性、特定振实密度和比表面积的天然石墨，由其作为制备原料，最后制备得到的改性天然石墨材料具有较高的各向同性，进而具有较优的倍率性能和循环性能。

Description

天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用 技术领域
本申请属于负极材料技术领域，涉及一种天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用。
背景技术
随着全球变暖加剧，控制CO 2释放量成为了人类社会刻不容缓的重大挑战。在交通领域，发展新能能源汽车是大势所趋，各国政府相继推出了各种优惠政策和补贴以推动新能源汽车发展，在政策推动下，以锂离子电池为动力电池的电动汽车快速发展。但是由于动力电池存在价格高、充电慢等问题，电动汽车至今没有完全实现商业化，如何降低动力电池价格和提升性能成为当前的研发重点。
动力锂离子电池电芯主要有负极、电解液、隔膜和正极组成，其中，正负极对电池的性能有决定性的影响，因此，动力电池研发的重点在于开发质廉价优的电极材料。对于负极材料，石墨材料依然处于主导位置，石墨依据来源可细分为人造和天然石墨，人造石墨需要经过超高温石墨化过程，使得其价格难以下降。天然石墨不需要高温石墨化过程，因此有着明显的成本优势，在3C领域占据着负极材料市场的主要地位，但是在将天然石墨应用于动力电池过程中其性能还存在着一些问题，特别是倍率性能。现阶段用天然石墨一般呈现较大片状，在电极制备压片过程中片状石墨会逐步与集流体平行，会大大降低材料的电解液透过能力，非常不利于电池的倍率性能，即使将片状石墨进行球形化处理，也很难将球形度做的很高。通常所说的球形石墨呈现椭圆状，在椭圆颗粒长轴方向通常也是鳞片的平行方向，压片过程中椭球形会形成长轴方向与集 流体平行，基于此制备的负极材料在极片石墨压实过程中依然大部分鳞片与集流体平行。因此，如何改善天然石墨的取向性，从而改善天然石墨的倍率性能是一个急需攻克的难题。
CN107195903A公开了一种锂离子动力电池用小粒径天然石墨负极材料及其制备方法，该发明通过在生产15-25μm天然石墨粉碎设备的成品出料口与尾料出料之间增加一个“二料口”，收集粒度范围5-25μm和振实密度大于0.65g/cm 3的石墨材料，再经过新整形、化学纯化、沥青包覆碳化，得到小粒径高容量天然石墨负极材料，但其首次库伦效率与倍率性能仍较差。CN106629702A公开了一种高循环天然石墨负极材料的加工方法，采用如下制备步骤：(1)混合：将天然石墨原料与改性剂按质量比100:0～30均匀混合，得混合物；(2)等静压处理；(3)粉碎；(4)表面改性；(5)冷却分级。该发明对天然石墨进行致密化改性，改性剂在外压作用下进入材料内部，填充空隙，经过热处理后，改性剂形成非晶炭或人造石墨的稳定结构。这一结构相比于天然石墨的高石墨化度层结构，对电解液的抗性更好，但所得石墨材料其首次库伦效率与容量保持率仍旧无法满足高性能石墨材料要求。CN106744916A公开了一种高倍率锂离子电池负极材料的改性方法，包括如下处理步骤：(1)原料混合：将树脂粉末与石墨原料按重量比1:100～15:100进行均匀混合；(2)中温炭化处理：在惰性气氛中，升温至600～1300℃，并在该温度下恒温1～4h；(3)冷却后分级处理，得改性锂离子电池石墨负极材料。该发明采用特定树脂对石墨颗粒进行包覆改性，制备锂离子电池负极材料，该方法制备的复合材料倍率性能及首次库伦效率不佳。
因此，需要开发一种天然石墨的制备方法，提高其各向同性，减少其取向 性，进而提高天然石墨的倍率性能和循环性能。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种天然石墨及由其制备得到的改性天然石墨材料、制备方法和应用。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供了一种天然石墨，所述天然石墨具有如下特征：
(1)粒度D50<10μm，D90/D10<2.5；
(2)002面间距为0.336-0.360，I 002/I 110≤35；
(3)0.6g/cc≤饱和振实密度<1.3g/cc；
(4)1.0m 2/g≤比表面积<10.0m 2/g。
本申请提供了一种具有特定粒度、特定取向性、特定振实密度和比表面积的天然石墨，由特定选择的天然石墨制备得到改性天然石墨材料会具有较高的各向同性，进而具有较优的倍率性能和循环性能。
本申请的粒度由粒度测试仪测试得到，002面间距等信息由XRD测试求得，通过氮气吸脱附测试得到其比表面积。
在本申请中，对天然石墨的限定缺一不可，只有选择上述限定的天然石墨才能制备得到性能优异的改性天然石墨材料。当天然石墨的平均粒径以及粒径分布不在本申请的限定范围内时，会造成加工过程中的固型效果不理想，粒径分布(D90/D10)过大，会降低改性天然石墨材料的倍率性能；当天然石墨的002面间距以及I 002/I 110不在本申请提供的范围内时，也会导致改性天然石墨材 料的倍率性能下降；当天然石墨的饱和振实密度不在本申请提供的范围内时，会影响改性天然石墨材料的加工性能；当天然石墨的比表面积不在本申请提供的范围内时，会影响改性天然石墨材料的首次库伦效率。
所述粒度D50<10μm，例如9μm、8.5μm、8μm、7μm、6μm、4μm等，D90/D10<2.5，例如2.47、2.45、2.4、2.38、2.35、2.2、2.0、1.8、1.5等。
所述I 002/I 110≤35，例如34、33.5、33.2、33、32.4、32、30等。
所述0.6g/cc≤饱和振实密度<1.3g/cc，例如0.65g/cc、0.7g/cc、0.75g/cc、0.8g/cc、0.85g/cc、0.9g/cc、1.0g/cc、1.1g/cc、1.2g/cc等。
所述1.0m 2/g≤比表面积<10.0m 2/g，例如2m 2/g、2.5m 2/g、3m 2/g、3.5m 2/g、4m 2/g、5m 2/g、5.5m 2/g、6m 2/g、7m 2/g、8m 2/g、9m 2/g等。
可选地，所述天然石墨由天然鳞片石墨经过粉碎所得或由微晶石墨经粉碎、整形所得。
本申请提供的天然石墨可以是天然鳞片石墨进行筛选，也可以通过制备方法制备得到。
第二方面，本申请提供了一种改性天然石墨材料，所述改性天然石墨材料的制备原料包括第一方面所述的天然石墨。
第三方面，本申请提供了第二方面所述的改性天然石墨材料的制备方法，所述制备方法为对天然石墨进行改性处理，得到所述改性天然石墨材料；
在本申请中，所述改性处理包括：对所述天然石墨依次进行固型、各向同性处理、碳化处理、粉碎。
对具有上述特征的天然石墨先进行粘结、固型，然后可以采用各向同性工艺处理，进一步提高天然石墨的各向同性，相对比与相关技术而言，本申请的 处理手法更能有效的获得各向同性程度较高的改性天然石墨。
可选地，所述固型用的固型剂为软化点为20-300℃(例如40℃、50℃、60℃、80℃、100℃、120℃、150℃、180℃、200℃、220℃、250℃、280℃等)的酚醛树脂、环氧树脂、石油树脂、煤沥青、石油沥青、中间相沥青、煤焦油或重质油中的任意一种或至少两种的组合。
可选地，所述天然石墨与所述固型剂的质量比为1:(0.05-1)，例如1:0.1、1:0.2、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9等。
可选地，所述固型在加热搅拌的情况下进行。
可选地，所述加热的温度为50-800℃，例如100℃、200℃、400℃、500℃、600℃、700℃等。
可选地，所述搅拌的时间为0-300min，例如1min、5min、10min、50min、80min、120min、150min、180min、200min、220min、250min、280min等。
可选地，所述各向同性处理包括冷等静压处理、热等静压处理或模压处理中的任意一种或至少两种的组合。
可选地，所述碳化处理的温度为1000-3000℃，例如1200℃、1500℃、1800℃、2000℃、2200℃、2500℃、2800℃等。
可选地，所述碳化处理在惰性气体环境下进行。
可选地，所述惰性气体为氦气、氖气、氩气、氮气或氪气中的任意一种或至少两种的组合。
可选地，所述制备方法还包括粉碎之后过筛。
可选地，过筛后产物的粒径为：7μm≤D50≤18μm，例如8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm等。
本申请的改性天然石墨材料制备工艺简单、易操作，成本低廉，具有较高的实用性。
第四方面，本申请提供了一种锂离子电池，所述锂离子电池包括第二方面所述的改性天然石墨材料。
可选地，所述锂离子电池的负极极片包括第二方面所述的改性天然石墨材料。
相对于相关技术，本申请具有以下有益效果：
(1)本申请提供了具有特定粒度、特定取向性、特定振实密度和比表面积的天然石墨，由其作为制备原料，最后制备得到的改性天然石墨材料具有较高的各向同性，进而具有较优的倍率性能和循环性能；
(2)对具有上述特征的天然石墨先进行粘结、固型，然后可以采用各向同性工艺处理，进一步提高天然石墨的各向同性，相对比于相关技术而言，本申请的处理手法更能有效的获得各向同性程度较高的改性天然石墨；
(3)本申请提供的制备方法得到的改性天然石墨材料常温5C/1C放电容量保持率超过94％，1C/1C充放电300次容量保持率超过90.2％。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
一种改性天然石墨材料，制备方法如下：
将天然石墨(D50＝6μm，D90/D10＝2.48，I 002/I 110≤33.2，饱和振实密度为 0.62g/cc，比表面积为9.4m 2/g)与石油沥青(软化点为140℃)以1:0.25的比例进行混合，然后将混合的物料投入到特定反应釜中进行搅拌加热，加热温度为360℃，并保温3小时，加热后的物料进行冷等静压处理，处理压力为120MPa，时间为2min。将等静压后的产品进行2800℃碳化处理，之后将物料粉碎至原料近似粒径，过筛，得到D50为8.3μm的改性天然石墨材料。
实施例2-5
与实施例1的区别仅在于，在本实施例中，天然石墨与煤沥青的的质量比为1:0.05(实施例2)、1:1(实施例3)、1:0.01(实施例4)、1:2(实施例5)。
实施例6
与实施例1的区别仅在于，在本实施例中，固型剂为酚醛树脂(软化点为110℃)。
实施例7
将天然石墨(D50＝8μm，D90/D10＝2.41，I 002/I 110≤34.2，饱和振实密度为0.76g/cc，比表面积为6.9m 2/g)与煤沥青(软化点为90℃)以1:0.3的比例进行混合，然后将混合的物料投入到特定反应釜中进行搅拌加热，加热温度为260℃，并保温3小时，加热后的物料进行冷等静压处理，处理压力为110MPa，时间为1min。将等静压后的产品进行2800℃碳化处理，之后将物料粉碎至原料近似粒径，过筛，得到D50为11.1μm的改性天然石墨材料。
实施例8
将天然石墨(D50＝9.8μm，D90/D10＝2.47，I 002/I 110＝34.8，振实密度为0.86g/cc，比表面积为6.1m 2/g)与煤沥青(软化点为180℃)以1:0.2的比例进行混合，然后将混合的物料投入到特定反应釜中进行搅拌加热，加热温度为360℃， 并保温3小时，加热后的物料进行冷等静压处理，处理压力为80MPa，时间为1min。将等静压后的产品进行1200℃碳化处理，之后将物料粉碎至原料近似粒径，过筛，得到D50为12.8μm的改性天然石墨材料。
对比例1
与实施例1的区别仅在于，在本对比例中，天然石墨的D50＝15μm。
对比例2
与实施例1的区别仅在于，在本对比例中，天然石墨的D90/D10＝2.64。
对比例3
与实施例1的区别仅在于，在本对比例中，天然石墨的I 002/I 110＝48
对比例4
与实施例1的区别仅在于，在本对比例中，天然石墨的饱和振实密度为0.42g/cc。
对比例5
与实施例1的区别仅在于，在本对比例中，天然石墨的比表面积为12m 2/g。
性能测试
对实施例1-8以及对比例1-5制备的改性天然石墨材料粉体的测试，方法如下：
(1)粒度：利用粒度测试仪测试；
(2)XRD测试：利用XRD测试仪测试；
(3)比表面积测试：利用氮气吸脱附仪器测试；
将实施例1-8以及对比例1-5制备的改性天然石墨材料制成负极极片、电池，方法如下：
负极极片：将提供的改性天然石墨材料作为负极材料的负极活性物质，按照活性物质:导电剂:CMC:SBR＝95:1.5:1.5:2的质量比混合均匀后，涂覆在铜箔集流体上，经干燥得到负极极片。
电池：将提供的改性天然石墨材料、导电剂、CMC和SBR按95:1.5:1.5:2的质量比混合后涂覆于铜箔，得到负极极片；将正极活性物质LiCoO 2、导电剂、PVDF按96.5:2:1.5的质量比混合均匀后涂覆于铝箔，得到正极极片；电解液为1mol/L LiPF 6+EC+EMC，隔膜为聚乙/丙烯复合微孔膜。
将制备得到的负极极片和电池进行性能测试，方法如下：
(4)扣电容量和首次库伦效率：将制备得到的负极极片进行扣式电池测试，电池组装在氩气手套箱中进行，以金属锂片为负极，电解液为1mol/L LiPF 6+EC+EMC，隔膜为聚乙/丙烯复合微孔膜，电化学性能在新威电池测试柜(5V,1A)上进行，充放电电压为0.01-1.5V，充放电速率为0.1C，测试其扣电容量和首次库伦效率；
(5)全电池测试：将制备好的负极和正极极片组装成18650圆柱电池，分容后进行后续测试。
5C/1C放电容量保持率测试方法为：a.分容后电池采用1C充电、1C放电连续进行三次，取三次放电平均值为1C放电容量，之后使用同样的电池进行1C充电，5C放电，连续进行5次，取最后三次放电平均值作为5C放电容量；5C/1C放电容量保持率即为5C放电容量除以1C放电容量；
1C/1C容量保持率测试方法为：1C充电、1C放电连续不断进行充放电300周，每次充放电完成后均间隔1分钟。
测试结果见表1：
表1
Figure PCTCN2019098885-appb-000001
由实施例和测试结果可知，本申请提供的改性天然石墨材料的扣电容量在348mAh/g以上，首次库伦效率在90.2％以上，5C/1C放电容量保持率在94％以上，1C/1C放电容量保持率在91％以上。由实施例1-3和实施例4-5的对比可知，当本申请的天然石墨和固型剂的质量比为1:(0.05-1)时，最后得到的材料具有更好的性能。由实施例1和对比例1-5的对比可知，当选用的制备原料不在本申请限定的范围内时，虽然扣电容量和首次库伦效率相差不大，但是本申请得到的改性天然石墨材料具有更好的倍率性能。因此，只有选用本申请限定的天然石墨并且利用本申请提供的制备方法制备得到的改性天然石墨材料的性能更优。
申请人声明，本申请通过上述实施例来说明本申请的天然石墨及由其制备 得到的改性天然石墨材料、制备方法和应用，但本申请并不局限于上述详细方法，即不意味着本申请必须依赖上述详细方法才能实施。

Claims (11)

  1. 一种天然石墨，其中，所述天然石墨具有如下特征：
    (1)粒度D50<10μm，D90/D10<2.5；
    (2)002面间距为0.336-0.360，I 002/I 110≤35；
    (3)0.6g/cc≤饱和振实密度<1.3g/cc；
    (4)1.0m 2/g≤比表面积<10.0m 2/g。
  2. 根据权利要求1所述的天然石墨，其中，所述天然石墨由天然鳞片石墨经过粉碎所得或由微晶石墨经粉碎、整形所得。
  3. 一种改性天然石墨材料，其中，所述改性天然石墨材料的制备原料包括权利要求1或2所述的天然石墨。
  4. 根据权利要求3所述的改性天然石墨材料的制备方法，其中，所述制备方法为对如权利要求1或2所述的天然石墨进行改性处理，得到所述改性天然石墨材料；
    可选地，所述改性处理包括：对所述天然石墨依次进行固型、各向同性处理、碳化处理、粉碎。
  5. 根据权利要求4所述的制备方法，其中，所述固型用的固型剂为软化点为20-300℃的酚醛树脂、环氧树脂、石油树脂、煤沥青、石油沥青、中间相沥青、煤焦油或重质油中的任意一种或至少两种的组合。
  6. 根据权利要求4所述的制备方法，其中，所述天然石墨与所述固型剂的质量比为1:(0.05-1)。
  7. 根据权利要求4-6中的任一项所述的制备方法，其中，所述固型在加热搅拌的情况下进行；
    可选地，所述加热的温度为50-800℃；
    可选地，所述搅拌的时间为0-300min；
    可选地，所述各向同性处理包括冷等静压处理、热等静压处理或模压处理中的任意一种或至少两种的组合。
  8. 根据权利要求4-7中的任一项所述的制备方法，其中，所述碳化处理的温度为1000-3000℃；
    可选地，所述碳化处理在惰性气体环境下进行；
    可选地，所述惰性气体为氦气、氖气、氩气、氮气或氪气中的任意一种或至少两种的组合。
  9. 根据权利要求4-8中的任一项所述的制备方法，其中，所述制备方法还包括粉碎之后过筛；
    可选地，过筛后产物的粒径为：7μm≤D50≤18μm。
  10. 一种锂离子电池，其中，所述锂离子电池包括如权利要求3所述的改性天然石墨材料。
  11. 如权利要求10所述的锂离子电池，其中，所述锂离子电池的负极极片包括如权利要求3所述的改性天然石墨材料。
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