WO2017107806A1 - Method for preparing lithium-ion battery positive-electrode paste - Google Patents

Method for preparing lithium-ion battery positive-electrode paste Download PDF

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WO2017107806A1
WO2017107806A1 PCT/CN2016/109632 CN2016109632W WO2017107806A1 WO 2017107806 A1 WO2017107806 A1 WO 2017107806A1 CN 2016109632 W CN2016109632 W CN 2016109632W WO 2017107806 A1 WO2017107806 A1 WO 2017107806A1
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speed
battery
ion battery
low
positive electrode
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PCT/CN2016/109632
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French (fr)
Chinese (zh)
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王海波
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苏州格瑞动力电源科技有限公司
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 invention relates to a preparation method of a positive electrode sheet for a lithium ion battery.
  • Lithium-ion batteries are widely used in portable devices such as mobile phones, camcorders, and notebook computers because of their high operating voltage, high specific energy, long cycle life, low self-discharge rate, no memory effect, and environmental friendliness.
  • the lithium ion battery is mainly composed of a positive electrode material, a negative electrode material, a separator material and an electrolyte.
  • the performance of the positive electrode material directly affects various performance indexes of the lithium ion battery, and occupies a core position in the lithium ion battery.
  • the capacitance, electrical conductivity and safety of the lithium ion battery can be improved by adding a micro-conductive material such as graphene or carbon nanotube to the positive electrode material.
  • the object of the present invention is to overcome the defects existing in the prior art, and to provide a preparation method of a positive electrode sheet for a lithium ion battery, which can improve the dispersion performance of the ultra-fine conductive material, thereby effectively improving the capacity, cycle performance and safety of the battery core. performance.
  • the technical solution of the present invention includes the following steps:
  • the amount of glue is 1-3% of the total amount of the cathode material, first add a part, according to the low speed (usually 50-100r/min), medium speed (usually 1000r/min), low speed program agitation 0.5-1h, 0.5-2h, 0.5-1h;
  • NMP N-methylpyrrolidone
  • the positive electrode active material is any one of lithium cobaltate, a ternary material, lithium manganate, and lithium iron phosphate.
  • the invention has the advantages and beneficial effects that the dispersing performance of the micro-conductive material such as graphene or carbon nanotubes is effectively improved, the capacity and cycle performance of the lithium ion battery cell can be effectively improved, and the heat dissipation performance of the battery can be improved in particular. Thereby improving the safety performance of the battery.
  • the amount of the glue liquid is 3% of the total amount of the cathode material, first add a part, stir at 100r/min for 0.5h, stir at 1000r/min for 1h, 50r Stir for 1 h under /min conditions;
  • the positive electrode active material is lithium cobaltate, ternary material or lithium manganate, the viscosity is adjusted to 2000-10000 CPS, and if the positive active material is ferric manganese phosphate, the viscosity is adjusted to 8000. -12000 CPS;

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Disclosed is a method for preparing a lithium-ion battery positive-electrode paste, the steps being as follows: first, mixing together a positive-electrode reactive material, a conductive agent, and a conductive graphite in a certain ratio; dry-blending in a dispersing machine, then adding a dispersed graphene adhesive or carbon nanotube adhesive in a certain ratio; stirring for different times according to a low-speed, medium-speed, low-speed program; then adding the remaining adhesive and stirring according to a low-speed, high-speed, low-speed program for different periods of time; then adding NMP to adjust the viscosity of the slurry, and removing bubbles, discharging material, coating, fabricating plates, and producing the battery cell. The present invention effectively improves the dispersibility of micro-conductive materials such as graphene and carbon nanotubes, effectively increases battery-cell capacity and improves cycle performance, especially the heat dissipation performance of the battery, thereby improving the safety performance of the battery.

Description

一种锂离子电池正极浆料的制备方法Method for preparing lithium ion battery positive electrode slurry 技术领域Technical field
本发明涉及一种锂离子电池正极片的制备方法。The invention relates to a preparation method of a positive electrode sheet for a lithium ion battery.
背景技术Background technique
锂离子电池由于具有工作电压高、比能量大、循环寿命长、自放电率低、无记忆效应及对环境友好等优点，不仅被广泛应用于移动电话、摄像机、笔记本电脑等便携式设备，还被列为电动汽车、航天、军事及大型储能设备的候选电源。锂离子电池主要由正极材料、负极材料、隔离材料和电解液等构成，正极材料的性能直接影响了锂离子电池的各项性能指标，在锂离子电池中占据核心地位。虽然锂离子电池正极材料的市场前景十分乐观，但其还存在一定的技术瓶颈，尤其是它的电容量高与安全性能强的优势还未充分发挥出来。通过在正极材料中加入石墨烯或纳米碳管等超微导电材料可提高锂离子电池的电容量、导电性能以及安全性。Lithium-ion batteries are widely used in portable devices such as mobile phones, camcorders, and notebook computers because of their high operating voltage, high specific energy, long cycle life, low self-discharge rate, no memory effect, and environmental friendliness. Listed as a candidate power source for electric vehicles, aerospace, military and large energy storage equipment. The lithium ion battery is mainly composed of a positive electrode material, a negative electrode material, a separator material and an electrolyte. The performance of the positive electrode material directly affects various performance indexes of the lithium ion battery, and occupies a core position in the lithium ion battery. Although the market prospect of lithium ion battery cathode material is very optimistic, it still has certain technical bottlenecks, especially its advantages of high capacitance and strong safety performance have not been fully exerted. The capacitance, electrical conductivity and safety of the lithium ion battery can be improved by adding a micro-conductive material such as graphene or carbon nanotube to the positive electrode material.
然而，这些超微导电材料都难以均匀地分散在电极活性物质中，限制了其功能的充分发挥。现有的锂离子电池正极材料的搅拌工艺均无法使超微导电材料得到充分地分散。However, it is difficult for these ultrafine conductive materials to be uniformly dispersed in the electrode active material, which limits the full function of the functions. The stirring process of the existing lithium ion battery positive electrode material cannot fully disperse the ultrafine conductive material.
发明内容Summary of the invention
本发明的目的在于克服现有技术中存在的缺陷，提供了一种锂离子电池正极片的制备方法，可提高超微导电材料的分散性能，进而有效地提高电芯的容量、循环性能和安全性能。The object of the present invention is to overcome the defects existing in the prior art, and to provide a preparation method of a positive electrode sheet for a lithium ion battery, which can improve the dispersion performance of the ultra-fine conductive material, thereby effectively improving the capacity, cycle performance and safety of the battery core. performance.
为实现上述目的，本发明的技术方案包括以下步骤：To achieve the above object, the technical solution of the present invention includes the following steps:
1)把正极活性物质材料、导电剂、导电石墨按(88-95)∶(1-2)∶(0-1)的比例(以重量百分比计)混合，用分散机干 混；1) Mix the positive electrode active material, the conductive agent, and the conductive graphite in a ratio of (88-95):(1-2):(0-1) (in weight percent), and dry with a disperser Mixed
2)向其中加入已经分散好的超微导电材料胶液，可以是石墨烯胶液或纳米碳管胶液，胶液的量为正极材料总量的1-3％，先加入一部分，按低速(通常为50-100r/min)、中速(通常为1000r/min)、低速程序分别搅拌0.5-1h，0.5-2h，0.5-1h；2) Adding the already dispersed ultra-fine conductive material glue, which may be graphene glue or carbon nanotube glue, the amount of glue is 1-3% of the total amount of the cathode material, first add a part, according to the low speed (usually 50-100r/min), medium speed (usually 1000r/min), low speed program agitation 0.5-1h, 0.5-2h, 0.5-1h;
3)加入剩下所述的胶液，按低速、高速(通常为1000r/min)、低速程序分别搅拌0.5-1h，1-2h，0.5-1h；3) adding the remaining glue, stirring at low speed, high speed (usually 1000r / min), low speed program 0.5-1h, 1-2h, 0.5-1h;
4)加入N-甲基吡咯烷酮(NMP)调整浆料粘度，若正极活性物质材料为钴酸锂、三元材料或锰酸锂，则粘度调整至2000-10000CPS，若正极活性物质材料为磷酸铁锰，则粘度调整至8000-12000CPS；4) Adding N-methylpyrrolidone (NMP) to adjust the viscosity of the slurry. If the material of the positive electrode active material is lithium cobaltate, ternary material or lithium manganate, the viscosity is adjusted to 2000-10000 CPS, and if the positive electrode active material is iron phosphate Manganese, the viscosity is adjusted to 8000-12000 CPS;
5)抽泡、出料、涂布、制片，制作电芯；5) foaming, discharging, coating, filming, making batteries;
作为优选地，所述的正极活性物质材料为钴酸锂、三元材料、锰酸锂、磷酸铁锂中的任一种。Preferably, the positive electrode active material is any one of lithium cobaltate, a ternary material, lithium manganate, and lithium iron phosphate.
本发明的优点和有益效果在于：有效地改善了石墨烯或纳米碳管等微导电材料的分散性能，可以有效地提高锂离子电池电芯的容量、循环性能，特别能够改善电池的散热性能，从而提高电池的安全性能。The invention has the advantages and beneficial effects that the dispersing performance of the micro-conductive material such as graphene or carbon nanotubes is effectively improved, the capacity and cycle performance of the lithium ion battery cell can be effectively improved, and the heat dissipation performance of the battery can be improved in particular. Thereby improving the safety performance of the battery.
具体实施方式detailed description
下面结合实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。The specific embodiments of the present invention are further described below in conjunction with the embodiments. The following examples are only intended to more clearly illustrate the technical solutions of the present invention, and are not intended to limit the scope of the present invention.
本发明具体实施的技术方案是： The technical solution specifically implemented by the present invention is:
1)把正极活性物质材料、导电剂、导电石墨按92∶2∶1的比例混合，用分散机干混；1) mixing the positive electrode active material material, the conductive agent, and the conductive graphite in a ratio of 92:2:1, and dry-mixing with a disperser;
2)向其中加入已经分散好的石墨烯胶液，胶液的量为正极材料总量的3％，先加入一部分，在100r/min条件下搅拌0.5h，1000r/min条件下搅拌1h，50r/min条件下搅拌1h；2) Add the already dispersed graphene glue solution, the amount of the glue liquid is 3% of the total amount of the cathode material, first add a part, stir at 100r/min for 0.5h, stir at 1000r/min for 1h, 50r Stir for 1 h under /min conditions;
3)加入剩下的胶液，在100r/min条件下搅拌0.5h，3000r/min条件下搅拌2h，50r/min条件下搅拌1h；3) adding the remaining glue, stirring at 100r / min for 0.5h, stirring at 3000r / min for 2h, stirring at 50r / min for 1h;
4)加入NMP调整浆料粘度，若正极活性物质材料为钴酸锂、三元材料或锰酸锂，则粘度调整至2000-10000CPS，若正极活性物质材料为磷酸铁锰，则粘度调整至8000-12000CPS；4) Adding NMP to adjust the viscosity of the slurry. If the positive electrode active material is lithium cobaltate, ternary material or lithium manganate, the viscosity is adjusted to 2000-10000 CPS, and if the positive active material is ferric manganese phosphate, the viscosity is adjusted to 8000. -12000 CPS;
5)抽泡、出料、涂布、制片，制作电芯。5) Foaming, discharging, coating, filming, and making batteries.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make several improvements and retouchings without departing from the technical principles of the present invention. It should also be considered as the scope of protection of the present invention.

Claims (2)

  1. 一种锂离子电池正极片的制备方法，其特征在于，包括如下步骤：A method for preparing a positive electrode sheet for a lithium ion battery, comprising the steps of:
    1)把正极活性物质材料、导电剂、导电石墨按(88％-95％)∶(1-2％)∶(0-1％)的比例混合，用分散机干混；1) mixing the positive electrode active material material, the conductive agent, and the conductive graphite in a ratio of (88% - 95%) : (1-2%) : (0-1%), and dry-mixing with a disperser;
    2)向其中加入部分已经分散好的超微导电材料胶液，按低速、中速、低速程序分别搅拌0.5-1h，0.5-2h，0.5-1h；2) adding some of the already dispersed ultra-fine conductive material glue, and stirring 0.5-1h, 0.5-2h, 0.5-1h according to the low speed, medium speed and low speed programs;
    3)加入剩下所述的胶液，按低速、高速、低速程序分别搅拌0.5-1h，1-2h，0.5-1h；3) adding the remaining glue, stirring 0.5-1h, 1-2h, 0.5-1h according to low speed, high speed and low speed program;
    4)加入NMP调整浆料粘度；4) adding NMP to adjust the viscosity of the slurry;
    5)抽泡、出料、涂布、制片，制作电芯；5) foaming, discharging, coating, filming, making batteries;
  2. 根据权利要求1中所述的锂离子电池正极片的制备方法，其特征在于，所述的正极活性物质材料为钴酸锂、三元材料、锰酸锂、磷酸铁锂中的任一种。 The method for producing a positive electrode sheet for a lithium ion battery according to claim 1, wherein the positive electrode active material is any one of lithium cobaltate, a ternary material, lithium manganate, and lithium iron phosphate.
PCT/CN2016/109632 2015-12-25 2016-12-13 Method for preparing lithium-ion battery positive-electrode paste WO2017107806A1 (en)

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CN113260737A (en) * 2019-04-26 2021-08-13 松下知识产权经营株式会社 Membrane electrode assembly, electrochemical device, and electrochemical system
CN114005983A (en) * 2021-10-14 2022-02-01 华中科技大学 Preparation method of additive-free vanadium pentoxide/carbon electrode slurry and product

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CN109244464A (en) * 2018-09-06 2019-01-18 中国航发北京航空材料研究院 A kind of graphene anode sizing agent and efficient controllable method for preparing
CN110061222B (en) * 2019-04-30 2021-07-16 郑州中科新兴产业技术研究院 Preparation method and application of lithium battery slurry

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CN114005983B (en) * 2021-10-14 2023-04-07 华中科技大学 Preparation method of additive-free vanadium pentoxide/carbon electrode slurry and product

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