WO2016110113A1 - Procédé de préparation de feuille d'électrode négative de pile lithium-ion utilisant un tissu de fibres de carbone comme matrice - Google Patents

Procédé de préparation de feuille d'électrode négative de pile lithium-ion utilisant un tissu de fibres de carbone comme matrice Download PDF

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Publication number
WO2016110113A1
WO2016110113A1 PCT/CN2015/088159 CN2015088159W WO2016110113A1 WO 2016110113 A1 WO2016110113 A1 WO 2016110113A1 CN 2015088159 W CN2015088159 W CN 2015088159W WO 2016110113 A1 WO2016110113 A1 WO 2016110113A1
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WIPO (PCT)
Prior art keywords
negative electrode
carbon fiber
electrode sheet
lithium ion
fiber cloth
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PCT/CN2015/088159
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English (en)
Chinese (zh)
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田东
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田东
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Publication of WO2016110113A1 publication Critical patent/WO2016110113A1/fr

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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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 negative electrode sheet for a lithium ion battery, in particular to a method for preparing a negative electrode sheet by replacing a conventional negative electrode sheet base copper foil with a carbon fiber cloth.
  • Carbon fiber cloth is a new type of carbon fiber derivative, which is made by using carbon fiber raw silk through the process of cutting, spinning and weaving.
  • the raw materials there are mainly PAN-based carbon fiber cloths (more than 90% of the carbon fiber cloths on the market), viscose-based carbon fiber cloths, and pitch-based carbon fiber cloths.
  • the weaving method the main organic woven carbon fiber cloth, knitted carbon fiber cloth, woven carbon fiber cloth, carbon fiber prepreg, carbon fiber non-woven fabric and the like. It is mainly used for reinforcement and repair of various structural types and structural shapes such as building bridges and tunnels, and structural reinforcement of joints.
  • the utility model has the advantages of convenient construction, no need for large-scale machine equipment, no wet operation, no need for hot fire, no need for on-site fixed facilities, less construction occupied space and high construction efficiency. High durability, because it does not rust, it is very suitable for use in high acid, alkali, salt and atmospheric corrosive environments.
  • Lithium-ion batteries consist of a positive electrode, a negative electrode, an electrolyte, a separator, and other ancillary materials.
  • the positive and negative electrodes of lithium-ion battery are composed of two different lithium ion intercalation compounds.
  • When charging lithium ions are deintercalated from the positive electrode and inserted into the negative electrode through the electrolyte.
  • the negative electrode is in a lithium-rich state, and the positive electrode is in a depleted state. On discharge, the opposite is true.
  • the electrolyte is embedded in the positive electrode, and the positive electrode is in a lithium-rich state, which is what people call a "rocking chair battery.”
  • the preparation process of the lithium ion battery is that the positive and negative active materials are respectively coated on the aluminum foil and the copper foil substrate by pulping, and finally obtained by rolling, tableting, assembling, injecting, forming and the like.
  • a copper foil is generally used for a negative electrode substrate, and is coated on a copper foil by mixing a negative electrode material with a conductive agent and a binder, but since the negative electrode material is generally a non-metallic graphite-based carbon material, A common problem in the industry is that the negative active material and the copper foil have problems such as loosening of the material due to poor adhesion, powder removal, and poor overall flexibility of the negative electrode sheet.
  • binder component CMC, SBR or PVDF
  • the present invention is directed to solving the above technical problems, and a method for preparing a negative electrode tab of a lithium ion battery using a carbon fiber cloth as a negative electrode substrate.
  • a method for preparing a negative electrode sheet for a lithium ion battery based on a carbon fiber cloth the preparation steps are as follows:
  • the pre-oxidized wire cloth is heated under the protection of an inert gas at a temperature increase rate of 1 to 20 ° C / min to 700 ° C to 1300 ° C, maintained at a high temperature for 0.5 to 5 hours, and then cooled to room temperature;
  • the softening point of the carbon fiber spinnable asphalt is 150 to 300 ° C
  • the amount of residual carbon is ⁇ 60%
  • the quinoline insoluble matter (QI) is ⁇ 3.0%. If the amount of residual carbon in the asphalt is too high, the production cost of the asphalt will increase, and the amount of residual carbon will be too low, indicating that the volatile content in the asphalt is high, which will reduce the strength and yield of the carbon fiber produced.
  • the diameter of the asphalt fiber strand is between 4 and 30 ⁇ m, and the diameter is too small, which increases the difficulty of spinning, and the spun yarn is easily broken, resulting in the fiber cloth produced in the later stage having too low strength and too large diameter, which will increase.
  • the heating rate of the pre-oxidation of the raw silk is controlled to 0.5 to 5 ° C / min, and the temperature is raised to 10 to 50 ° C above the softening point of the asphalt. If the heating rate is too high, the raw silk will be melted, and the temperature will be too low to achieve the effect of oxidation. If the temperature is too high, the yield of the carbonization treatment will be lowered.
  • the thickness of the pre-oxidized silk cloth is 50 to 200 ⁇ m, and the thickness is too small, which causes the unit volume capacity of the negative electrode sheet to decrease, and the thickness is too large, which may affect the transfer of the later battery core.
  • the temperature of the high temperature graphitization treatment is 2600 ° C or higher.
  • the preparation of the negative electrode slurry and the size of the slit into small pieces are determined according to different lithium ion battery models, and the specific process requirements are well known to those skilled in the art, and are not described herein.
  • the commonly used method of tab welding is to directly solder the nickel tab of the metal material to the base of the negative electrode-copper foil by ultrasonic or laser.
  • the negative electrode sheet of the present invention is a non-metal material, and the conventional soldering method cannot be used.
  • the present invention bonds nickel tabs and carbon fiber cloth by means of conductive adhesive or soldering having adhesive properties. At the same time, the position of the tab can be bonded to any position of the pole piece according to the actual process requirements.
  • non-metallic carbon fiber cloth instead of metal copper foil is technically a bold innovation and breakthrough.
  • the carbon fiber conductive and heat dissipation performance after graphitization is more advantageous than copper foil, and because of the copper as the matrix.
  • the thickness of the foil is only about 10 ⁇ m, and the strength is extremely poor.
  • the carbon fiber cloth is used as the base body, and it is not easy to have broken pieces and no curling;
  • the carbon fiber cloth and the negative electrode active material belong to the same graphite. In addition to being a matrix, it can also participate as a part of the active material, participate in the insertion and extraction of lithium ions, and increase the volumetric energy density of the pole piece;
  • the carbon fiber cloth is a non-metal material, and has good bonding performance with graphite.
  • the proportion of the binder component can be reduced, and the content of the active material can be further increased;
  • the carbon fiber filaments in the carbon fiber cloth are intricately interlaced to form a good conductive network, and the electrical conductivity is excellent.
  • the conductive paste may be added during the configuration of the negative electrode slurry or added less than normal, and the resulting negative electrode sheet still has good. Conductivity, the battery has a lower internal resistance;
  • the invention solves the technical problem of bonding the polar ear and the pole piece.
  • the advantage is that the conductive ear or the soldering method can be placed at any position of the pole piece to meet the lithium ion battery with special process requirements.
  • FIG. 1 is a schematic view showing the structure of a negative electrode sheet using a carbon fiber cloth as a substrate.
  • the carbon fiber spinnable pitch having a softening point of 250 ° C is heated to 280 ° C to melt into a liquid having a flowing state, and the spinneret of the melt spinning machine is adjusted to obtain a pitch fiber strand having a diameter of 20 ⁇ 1 ⁇ m, and the raw yarn is Empty
  • the gas was heated to 240 ° C at a heating rate of 2 ° C / min, and oxidized for 3 hours.
  • the oxidized raw yarn was passed through a slitting and spinning fabric to obtain a pre-oxidized silk cloth, and the thickness was controlled at 100 ⁇ 3 ⁇ m.
  • the areal density was controlled at 19.6 ⁇ 0.5 mg/cm2, and the pre-oxidized wire was heated under the protection of an inert gas at a heating rate of 10 ° C/min to 900 ° C, maintained at a high temperature for 2 hours, and then cooled to room temperature.
  • the carbonized pre-oxidized silk cloth is further graphitized at a high temperature, and the finally obtained carbon fiber cloth has a thickness of 90 ⁇ 3 ⁇ m and an areal density of 11.8 ⁇ 0.5 mg/cm 2 .
  • the positive electrode piece of 56 ⁇ 0.1mm the positive and negative electrode pieces are wound, injected, sealed, and formed into a 18650 cylindrical battery.
  • the separator is Celgard 2400, and the electrolyte is 1M LiPF6/DMC: EC: DEC.
  • the battery detection device performs electrical performance test, and the test results are shown in Table 1.
  • the carbon fiber spinnable pitch with a softening point of 200 ° C is heated to 250 ° C to melt into a liquid having a flowing state, and the spinneret of the melt spinning machine is adjusted to receive a pitch fiber strand having a diameter of 6 ⁇ 1 ⁇ m, and the raw yarn is
  • the temperature was raised to 230 ° C in the air at a heating rate of 1.5 ° C / min, and the oxidation treatment was carried out for 14 hours.
  • the oxidized raw yarn was passed through a slitting and spinning fabric to obtain a pre-oxidized silk cloth, and the thickness was controlled at 85 ⁇ 3 ⁇ m.
  • the areal density was controlled at 16.7 ⁇ 0.5 mg/cm2, and the pre-oxidized wire was heated under the protection of an inert gas at a temperature increase rate of 5 ° C/min to 850 ° C, maintained at a high temperature for 1 hour, and then cooled to room temperature.
  • the carbonized pre-oxidized silk cloth was further graphitized at a high temperature, and the finally obtained carbon fiber cloth had a thickness of 75 ⁇ 3 ⁇ m and an areal density of 9.4 ⁇ 0.5 mg/cm 2 .
  • the positive electrode piece of 56 ⁇ 0.1mm the positive and negative electrode pieces are wound, injected, sealed, and formed into a 18650 cylindrical battery.
  • the separator is Celgard 2400, and the electrolyte is 1M LiPF6/DMC: EC: DEC.
  • the power battery detection device performs electrical performance detection, and the test results are shown in Table 1.
  • a copper foil was used as the substrate, and other conditions were the same as those in Example 1.
  • the negative electrode tab was prepared, and the test method and the positive electrode tab were the same as in Example 1. The test results are shown in Table 1.
  • a copper foil was used as the substrate, and other conditions were the same as those in Example 2.
  • the negative electrode tab was prepared, and the test method and the positive electrode tab were the same as in Example 2. The test results are shown in Table 1.
  • Table 1 compares the performance of negative electrode materials in different examples and comparative examples.
  • the carbon fiber cloth of the present invention is used as the negative electrode pole piece base, and the battery obtained by using the copper foil-based negative electrode pole piece has a cycle, a charge rate charging, and a battery internal resistance. Better performance.

Abstract

L'invention concerne un procédé de préparation d'une feuille d'électrode négative de pile au lithium-ion utilisant un tissu de fibres de carbone comme matrice, le procédé consistant : à utiliser un tissu de fibres de carbone en remplacement d'une matrice de feuille d'électrode négative classique, telle qu'une feuille de cuivre, et à utiliser un brai de houille en fibres filable comme matière première ; à préparer et à pré-oxyder des filaments, et à effectuer un processus de rupture par étirage, un filage et un tissage afin d'obtenir un tissu de fibres pré-oxydées ; à effectuer une carbonisation et une graphitisation, une application de revêtement de suspension épaisse d'électrode négative, un laminage, un découpage en petits morceaux et un soudage de patte sur le tissu de fibres pré-oxydées afin d'obtenir une feuille d'électrode négative de pile lithium-ion. La feuille d'électrode négative de pile lithium-ion produite par le mode de réalisation de l'invention est complètement différente d'une feuille d'électrode négative de pile lithium-ion produite par un procédé de préparation classique. Ainsi, la fibre de carbone produite après un processus de graphitisation offre une meilleure conductivité électrique et une meilleure efficacité de dissipation thermique par comparaison avec une feuille de cuivre.
PCT/CN2015/088159 2015-01-08 2015-08-26 Procédé de préparation de feuille d'électrode négative de pile lithium-ion utilisant un tissu de fibres de carbone comme matrice WO2016110113A1 (fr)

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CN201510007803.4A CN104577041B (zh) 2015-01-08 2015-01-08 一种以碳纤维布为基体制备锂离子电池负极片的方法
CN201510007803.4 2015-01-08

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CN113113691A (zh) * 2021-04-06 2021-07-13 浙江天能新材料有限公司 一种废旧锂离子电池隔膜的干法脱粉设备
CN113972024A (zh) * 2021-10-29 2022-01-25 吉林聚能新型炭材料股份有限公司 一种碳基高长径比柔性导电材料及其制备方法

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CN104577041B (zh) * 2015-01-08 2017-01-11 深圳市玖创科技有限公司 一种以碳纤维布为基体制备锂离子电池负极片的方法
CN106450157A (zh) * 2016-11-14 2017-02-22 深圳拓邦股份有限公司 极片组件、电芯及电池
CN106531965A (zh) * 2016-11-30 2017-03-22 深圳拓邦股份有限公司 极片组件、电芯及电池
CN106784624B (zh) * 2016-12-16 2019-11-05 山东精工电子科技有限公司 一种锂离子电池正极片及其制备方法
CN107910486B (zh) * 2017-10-25 2021-12-03 肇庆中特能科技投资有限公司 碳纤维作为板栅与极耳的连接方法、碳纤维与极耳形成的电极板栅以及在化学电池中的应用
CN112420988A (zh) * 2020-11-05 2021-02-26 成都新柯力化工科技有限公司 一种锂电池氧化亚硅负极的预锂化方法

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CN104577041A (zh) * 2015-01-08 2015-04-29 田东 一种以碳纤维布为基体制备锂离子电池负极片的方法

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CN102560744A (zh) * 2011-12-21 2012-07-11 鞍山塞诺达碳纤维有限公司 一种通用级沥青基碳纤维的制备方法
CN104577041A (zh) * 2015-01-08 2015-04-29 田东 一种以碳纤维布为基体制备锂离子电池负极片的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113113691A (zh) * 2021-04-06 2021-07-13 浙江天能新材料有限公司 一种废旧锂离子电池隔膜的干法脱粉设备
CN113113691B (zh) * 2021-04-06 2023-03-14 浙江天能新材料有限公司 一种废旧锂离子电池隔膜的干法脱粉设备
CN113972024A (zh) * 2021-10-29 2022-01-25 吉林聚能新型炭材料股份有限公司 一种碳基高长径比柔性导电材料及其制备方法

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