CN115332470A - Modification method of negative electrode plate of lithium battery - Google Patents
Modification method of negative electrode plate of lithium battery Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- 238000002715 modification method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000003570 air Substances 0.000 claims abstract description 8
- 238000009832 plasma treatment Methods 0.000 claims description 14
- 229910021384 soft carbon Inorganic materials 0.000 claims description 13
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
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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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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Abstract
Description
技术领域technical field
本发明涉及一种改质方法，且特别涉及一种锂电池负极电极极板的改质方法。The invention relates to a modification method, and in particular to a method for modification of a negative electrode plate of a lithium battery.
背景技术Background technique
锂电池负极电极极板通常是使用天然石墨、人工石墨、软碳或硬碳等碳系材料，这些碳系材料的表面大多为疏水性质，液态电解液在极板表面较不容易润湿和渗透，因此，电极的使用面积会受到限制。尤其是当锂电池进行大电流充电时，会造成电池没办法充饱电即达到截止电压。Lithium battery negative electrode plates usually use carbon-based materials such as natural graphite, artificial graphite, soft carbon or hard carbon. The surfaces of these carbon-based materials are mostly hydrophobic, and the liquid electrolyte is less likely to wet and penetrate on the surface of the plate. , therefore, the use area of the electrode will be limited. Especially when the lithium battery is charged with a high current, it will cause the battery to be unable to fully charge and reach the cut-off voltage.
基于上述，发展出一种锂电池负极电极极板的改质方法，以提升锂电池的电性表现，为目前所需研究的重要课题。Based on the above, developing a method for modifying the negative electrode plate of a lithium battery to improve the electrical performance of the lithium battery is an important subject of current research.
发明内容Contents of the invention
本发明提供一种锂电池负极电极极板的改质方法，透过电浆对锂电池负极电极极板的极板进行电浆改质，以有效地提升锂电池的电性表现。The invention provides a method for modifying the negative electrode plate of a lithium battery, which uses plasma to modify the negative electrode plate of the lithium battery to effectively improve the electrical performance of the lithium battery.
本发明的锂电池负极电极极板的改质方法，包括以下步骤。将锂电池负极电极极板配置于大气电浆喷射束机台上，通入工作气体(氩气、氮气或空气等)并于大气环境下产生电浆，以电浆处理锂电池负极电极极板，使锂电池负极电极极板由疏水性改质为亲水性。The method for modifying the negative electrode plate of the lithium battery of the present invention comprises the following steps. Arrange the lithium battery negative electrode plate on the atmospheric plasma jet beam machine, pass through the working gas (argon, nitrogen or air, etc.) and generate plasma in the atmospheric environment, and use the plasma to treat the lithium battery negative electrode plate , so that the negative electrode plate of the lithium battery is modified from hydrophobicity to hydrophilicity.
在本发明的一实施例中，锂电池负极电极极板为碳系材料。In an embodiment of the present invention, the negative electrode plate of the lithium battery is made of carbon-based materials.
在本发明的一实施例中，碳系材料为石墨、软碳或硬碳。In an embodiment of the present invention, the carbon-based material is graphite, soft carbon or hard carbon.
在本发明的一实施例中，使锂电池负极电极极板由疏水性改质为亲水性的过程中，在锂电池负极电极极板的表面接上亲水官能基。In an embodiment of the present invention, during the process of modifying the negative electrode plate of the lithium battery from hydrophobicity to hydrophilicity, a hydrophilic functional group is attached to the surface of the negative electrode plate of the lithium battery.
在本发明的一实施例中，进行电浆处理的喷头与锂电池负极电极极板之间的距离为5mm至40mm。In an embodiment of the present invention, the distance between the nozzle for plasma treatment and the negative electrode plate of the lithium battery is 5 mm to 40 mm.
在本发明的一实施例中，对锂电池负极电极极板进行电浆处理35次至45次。In one embodiment of the present invention, the negative electrode plate of the lithium battery is subjected to plasma treatment for 35 to 45 times.
在本发明的一实施例中，当工作气体为氩气时，对锂电池负极电极极板进行电浆处理的反应温度为20℃至90℃。In an embodiment of the present invention, when the working gas is argon, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 20°C to 90°C.
在本发明的一实施例中，当工作气体为空气时，对锂电池负极电极极板进行电浆处理的反应温度为150℃至300℃。In an embodiment of the present invention, when the working gas is air, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 150°C to 300°C.
在本发明的一实施例中，当工作气体为氮气时，对锂电池负极电极极板进行电浆处理的反应温度为150℃至300℃。In an embodiment of the present invention, when the working gas is nitrogen, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 150°C to 300°C.
基于上述，本发明提供一种锂电池负极电极极板的改质方法，以电浆处理锂电池负极电极极板，使锂电池负极电极极板由疏水性改质为亲水性，如此一来，电解液可更加润湿极片，因此，有助于锂电池电性表现提升，不仅可提升理论电容量，也能改善稳定性，在高电流密度下充放电后，仍可维持极高的电容保有率。Based on the above, the present invention provides a method for modifying the negative electrode plate of a lithium battery. The negative electrode plate of the lithium battery is treated with plasma to modify the negative electrode plate of the lithium battery from hydrophobicity to hydrophilicity. , the electrolyte can wet the pole piece more, so it helps to improve the electrical performance of the lithium battery, not only can increase the theoretical capacity, but also improve the stability. After charging and discharging at a high current density, it can still maintain a very high Capacitance retention rate.
附图说明Description of drawings
图1为本发明的实例1至实例3、比较例以及铜箔比较的X光绕射分析(X-raydiffraction analysis,XRD)图谱。FIG. 1 is an X-ray diffraction analysis (X-ray diffraction analysis, XRD) spectrum of Examples 1 to 3 of the present invention, comparative examples and copper foil comparisons.
图2A至图2D分别为本发明比较例以及实例1至实例3的扫描式电子显微镜(Scanning Electron Microscope，SEM)图。2A to 2D are scanning electron microscope (Scanning Electron Microscope, SEM) images of Comparative Example and Examples 1 to 3 of the present invention, respectively.
图3为本发明比较例以及实例2的水接触角比较图。Fig. 3 is a comparative diagram of water contact angles of Comparative Example of the present invention and Example 2.
图4为本发明比较例以及实例1至实例3在不同电流密度下充放电的电容量比较图。FIG. 4 is a comparison chart of the capacitances of the comparative example of the present invention and examples 1 to 3 charged and discharged at different current densities.
图5为本发明比较例以及实例1至实例3的拉曼图谱。Fig. 5 is the Raman spectrum of the comparative example and examples 1 to 3 of the present invention.
图6、图7、图8及图9分别为本发明比较例以及实例1至实例3的X射线光电子光谱(X-ray Photoelectron Spectroscopy，XPS)图谱分析。Fig. 6, Fig. 7, Fig. 8 and Fig. 9 are the X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, XPS) spectrum analysis of the comparative example of the present invention and examples 1 to 3 respectively.
具体实施方式Detailed ways
以下，将详细描述本发明的实施例。然而，这些实施例为例示性，且本发明揭露不限于此。Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative, and the present disclosure is not limited thereto.
在本文中，由“一数值至另一数值”表示的范围，是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此，某一特定数值范围的记载，涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中说明文写出该任意数值和该较小数值范围一样。Herein, a range indicated by "one value to another value" is a general representation to avoid enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value within the numerical range and the smaller numerical range bounded by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value are written in the specification. same range.
本发明提供一种锂电池负极电极极板的改质方法，包括以下步骤。将锂电池负极极板配置于大气电浆喷射束机台上，通入工作气体(氩气、氮气或空气等)并于大气环境下产生电浆，以电浆处理锂电池负极电极极板，使锂电池负极电极极板由疏水性改质为亲水性。由于本发明是使用大气电浆喷射束机台，在大气环境下进行改质，因此，可使空气被引入，进而透过氮气进行活化(氮化)。The invention provides a method for modifying a negative electrode plate of a lithium battery, which comprises the following steps. Arrange the lithium battery negative electrode plate on the atmospheric plasma jet beam machine, pass through the working gas (argon, nitrogen or air, etc.) and generate plasma in the atmospheric environment, and use the plasma to treat the lithium battery negative electrode plate, Modify the negative electrode plate of lithium battery from hydrophobicity to hydrophilicity. Since the present invention uses an atmospheric plasma jet beam machine to carry out reforming in an atmospheric environment, air can be introduced and then activated (nitrided) through nitrogen.
在本实施例中，锂电池负极电极极板为碳系材料，碳系材料为石墨、软碳或硬碳，石墨可包括人工石墨或天然石墨。本发明使用的碳系材料较佳例如是软碳，具有高导电性及高储存能性质。此外，在制备锂电池负极电极极板极片的过程中，可更加入导电添加剂、黏着剂及电流收集器。导电添加剂可包括片状石墨、碳黑、奈米碳管、石墨烯、碳纤维或其组合；黏着剂可包括聚偏二氟乙烯(Polyvinylidene Fluoride，PVDF)、羧甲基纤维素(Carboxymethyl cellulose，CMC)、苯乙烯-丁二烯橡胶(Styrene-Butadiene Rubber，SBR)、聚酰亚胺(Polyimide，PI)或聚酰胺酸(Polyamide，PA)；电流收集器可包括铜箔、多孔镍或不锈钢。然而，本发明并不以此为限。In this embodiment, the negative electrode plate of the lithium battery is a carbon-based material, and the carbon-based material is graphite, soft carbon or hard carbon, and the graphite may include artificial graphite or natural graphite. The carbon-based material used in the present invention is preferably soft carbon, which has high electrical conductivity and high energy storage properties. In addition, conductive additives, adhesives and current collectors can be added during the process of preparing the negative electrode plate of the lithium battery. Conductive additives may include flake graphite, carbon black, carbon nanotubes, graphene, carbon fibers or combinations thereof; adhesives may include polyvinylidene fluoride (Polyvinylidene Fluoride, PVDF), carboxymethylcellulose (Carboxymethyl cellulose, CMC ), styrene-butadiene rubber (Styrene-Butadiene Rubber, SBR), polyimide (Polyimide, PI) or polyamic acid (Polyamide, PA); the current collector can include copper foil, porous nickel or stainless steel. However, the present invention is not limited thereto.
在本实施例中，进行电浆处理的喷头与锂电池负极电极极板之间的距离为约5mm至40mm。对锂电池负极电极极板进行电浆处理35次至45次。当工作气体为氩气时，对锂电池负极电极极板进行电浆处理的反应温度为20℃至90℃。当工作气体为空气时，对锂电池负极电极极板进行电浆处理的反应温度为150℃至300℃。当工作气体为氮气时，对锂电池负极电极极板进行电浆处理的反应温度为150℃至300℃。使锂电池负极电极极板由疏水性改质为亲水性的过程中，在锂电池负极电极极板的表面接上亲水官能基，亲水官能基可包括但不限于C-N、C-OH或C-H。In this embodiment, the distance between the nozzle for plasma treatment and the negative electrode plate of the lithium battery is about 5 mm to 40 mm. The negative electrode plate of the lithium battery is subjected to plasma treatment for 35 to 45 times. When the working gas is argon, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 20°C to 90°C. When the working gas is air, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 150°C to 300°C. When the working gas is nitrogen, the reaction temperature for performing plasma treatment on the negative electrode plate of the lithium battery is 150°C to 300°C. In the process of modifying the negative electrode plate of the lithium battery from hydrophobicity to hydrophilicity, a hydrophilic functional group is attached to the surface of the negative electrode plate of the lithium battery. The hydrophilic functional group may include but not limited to C-N, C-OH or C-H.
以下，藉由实验例来详细说明上述本发明所提出的锂电池负极电极极板的改质方法。然而，下述实验例并非用以限制本发明。Hereinafter, the method for modifying the negative electrode plate of the lithium battery proposed by the present invention will be described in detail by using an experimental example. However, the following experimental examples are not intended to limit the present invention.
实验例Experimental example
为了证明本发明所提出的锂电池负极电极极板的改质方法可使锂电池负极电极极板由疏水性改质为亲水性，进而提升锂电池电性表现，以下特别作此实验例。In order to prove that the modification method of the lithium battery negative electrode plate proposed by the present invention can modify the lithium battery negative electrode plate from hydrophobicity to hydrophilicity, thereby improving the electrical performance of the lithium battery, the following is a special example of this experiment.
实例1Example 1
以软碳0.92g、碳黑0.04g以及聚偏二氟乙烯(Polyvinylidene difluoride，PVDF)0.04g进行混浆、涂布制备软碳极片，将涂布好的极片以80℃烘干后，以氩气常压电浆、喷头与基材距离10mm进行极片改质20次，以1M的LiPF6的锂盐搭配碳酸乙烯酯(Ethylenecarbonate)/碳酸二甲酯(Dimethyl carbonate)/碳酸二乙酯(Diethyl carbonate)(1:1:1体积比)作为溶剂作为电解液组成钮扣型电池，测试电性表现。Mix 0.92g of soft carbon, 0.04g of carbon black, and 0.04g of polyvinylidene difluoride (PVDF) to prepare a soft carbon pole piece, and dry the coated pole piece at 80°C. The pole piece was modified 20 times with argon atmospheric pressure plasma, the distance between the nozzle and the substrate was 10mm, and the lithium salt of 1M LiPF6 was combined with ethylene carbonate (Ethylenecarbonate)/Dimethyl carbonate (Dimethyl carbonate)/Diethyl carbonate (Diethyl carbonate) (1:1:1 volume ratio) was used as a solvent as an electrolyte to form a button battery, and the electrical performance was tested.
实例2Example 2
以软碳0.92g、碳黑0.04g以及聚偏二氟乙烯(Polyvinylidene difluoride，PVDF)0.04g进行混浆、涂布制备软碳极片，将涂布好的极片以80℃烘干后，以氩气常压电浆、喷头与基材距离10mm进行极片改质40次，以1M的LiPF6的锂盐搭配碳酸乙烯酯(Ethylenecarbonate)/碳酸二甲酯(Dimethyl carbonate)/碳酸二乙酯(Diethyl carbonate)(1:1:1体积比)作为溶剂作为电解液组成钮扣型电池，测试电性表现。Mix 0.92g of soft carbon, 0.04g of carbon black, and 0.04g of polyvinylidene difluoride (PVDF) to prepare a soft carbon pole piece, and dry the coated pole piece at 80°C. The pole piece was modified 40 times with argon atmospheric pressure plasma, the distance between the nozzle and the substrate was 10mm, and 1M LiPF6 lithium salt was used with ethylene carbonate (Ethylenecarbonate)/Dimethyl carbonate (Dimethyl carbonate)/Diethyl carbonate (Diethyl carbonate) (1:1:1 volume ratio) was used as a solvent as an electrolyte to form a button battery, and the electrical performance was tested.
实例3Example 3
以软碳0.92g、碳黑0.04g以及聚偏二氟乙烯(Polyvinylidene difluoride，PVDF)0.04g进行混浆、涂布制备软碳极片，将涂布好的极片以80℃烘干后，以氩气常压电浆、喷头与基材距离10mm进行极片改质60次，以1M的LiPF6的锂盐搭配碳酸乙烯酯(Ethylenecarbonate)/碳酸二甲酯(Dimethyl carbonate)/碳酸二乙酯(Diethyl carbonate)(1:1:1体积比)作为溶剂作为电解液组成钮扣型电池，测试电性表现。Mix 0.92g of soft carbon, 0.04g of carbon black, and 0.04g of polyvinylidene difluoride (PVDF) to prepare a soft carbon pole piece, and dry the coated pole piece at 80°C. The pole piece was modified 60 times with argon atmospheric pressure plasma, the distance between the nozzle and the substrate was 10mm, and 1M LiPF6 lithium salt was used with ethylene carbonate/dimethyl carbonate/diethyl carbonate (Diethyl carbonate) (1:1:1 volume ratio) was used as a solvent as an electrolyte to form a button battery, and the electrical performance was tested.
比较例comparative example
以软碳0.92g、碳黑0.04g以及聚偏二氟乙烯(Polyvinylidene difluoride，PVDF)0.04g进行混浆、涂布制备软碳极片，将涂布好的极片以80℃烘干后，以1M的LiPF6的锂盐搭配碳酸乙烯酯(Ethylene carbonate)/碳酸二甲酯(Dimethyl carbonate)/碳酸二乙酯(Diethyl carbonate)(1:1:1体积比)作为溶剂作为电解液组成钮扣型电池，测试电性表现。Mix 0.92g of soft carbon, 0.04g of carbon black, and 0.04g of polyvinylidene difluoride (PVDF) to prepare a soft carbon pole piece, and dry the coated pole piece at 80°C. Use 1M LiPF6 lithium salt with Ethylene carbonate/Dimethyl carbonate/Diethyl carbonate (1:1:1 volume ratio) as the solvent to form a button Type battery, test electrical performance.
图1为本发明实例1至实例3、比较例以及铜箔比较的X光绕射分析(X-raydiffraction analysis,XRD)图谱。图2A至图2D分别为本发明比较例以及实例1至实例3的扫描式电子显微镜(Scanning Electron Microscope，SEM)图。图3为本发明比较例以及实例2的水接触角比较图。图4为本发明比较例以及实例1至实例3在不同电流密度下充放电的电容量比较图。图5为本发明比较例以及实例1至实例3的拉曼图谱。图6、图7、图8及图9分别为本发明比较例以及实例1至实例3的X射线光电子光谱(X-ray PhotoelectronSpectroscopy，XPS)图谱分析。FIG. 1 is an X-ray diffraction analysis (X-ray diffraction analysis, XRD) spectrum of Examples 1 to 3 of the present invention, comparative examples and copper foil comparisons. 2A to 2D are scanning electron microscope (Scanning Electron Microscope, SEM) images of Comparative Example and Examples 1 to 3 of the present invention, respectively. Fig. 3 is a comparative diagram of water contact angles of Comparative Example of the present invention and Example 2. FIG. 4 is a comparison chart of the capacitances of the comparative example of the present invention and examples 1 to 3 charged and discharged at different current densities. Fig. 5 is the Raman spectrum of the comparative example and examples 1 to 3 of the present invention. Fig. 6, Fig. 7, Fig. 8 and Fig. 9 are the X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, XPS) spectrum analysis of the comparative example of the present invention and examples 1 to 3 respectively.
由图3可得知，实例2的水接触角降低，因此，本发明的锂电池负极电极极板的改质方法透过电浆处理可有效地使锂电池负极电极极板由疏水性改质为亲水性。As can be seen from Figure 3, the water contact angle of Example 2 is reduced. Therefore, the method for modifying the lithium battery negative electrode plate of the present invention can effectively modify the lithium battery negative electrode plate by hydrophobicity through plasma treatment. is hydrophilic.
以下表1列出本发明比较例以及实例1至实例3在不同C数下的电容量。Table 1 below lists the capacitances of Comparative Examples of the present invention and Examples 1 to 3 at different C numbers.
表1Table 1
综上所述，本发明提供一种锂电池负极电极极板的改质方法，以电浆处理锂电池负极电极极板，使锂电池负极电极极板由疏水性改质为亲水性，其水接触角从112°降到60°。如此一来，电解液可更加润湿极片，因此，有助于锂电池电性表现提升，不仅可提升理论电容量，也能改善稳定性，在高电流密度下充放电后，仍可维持极高的电容保有率。进行充放电测试，在5A/g的电流密度下，可逆放电电容量提升到202mAh/g，约提升159％。本发明之锂电池负极电极极板的改质方法未来可应用于锂电池快充技术，特别是针对电动机车或电动车的动力电池进行电池性能的提升。In summary, the present invention provides a method for modifying the negative electrode plate of a lithium battery. The negative electrode plate of the lithium battery is treated with plasma, so that the negative electrode plate of the lithium battery is modified from hydrophobic to hydrophilic. The water contact angle decreased from 112° to 60°. In this way, the electrolyte can wet the pole piece more, so it helps to improve the electrical performance of the lithium battery. It can not only increase the theoretical capacity, but also improve the stability. After charging and discharging at a high current density, it can still maintain High capacitance retention rate. Carrying out charge and discharge tests, at a current density of 5A/g, the reversible discharge capacity increased to 202mAh/g, an increase of about 159%. The modification method of the negative electrode plate of the lithium battery of the present invention can be applied to the fast charging technology of the lithium battery in the future, especially for improving the battery performance of the power battery of an electric vehicle or an electric vehicle.
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.
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