WO2016110111A1 - Procédé de fabrication de tissu en fibre de carbone utilisé en tant que feuille de cathode de batterie lithium-ion - Google Patents

Procédé de fabrication de tissu en fibre de carbone utilisé en tant que feuille de cathode de batterie lithium-ion Download PDF

Info

Publication number
WO2016110111A1
WO2016110111A1 PCT/CN2015/088136 CN2015088136W WO2016110111A1 WO 2016110111 A1 WO2016110111 A1 WO 2016110111A1 CN 2015088136 W CN2015088136 W CN 2015088136W WO 2016110111 A1 WO2016110111 A1 WO 2016110111A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon fiber
lithium ion
ion battery
negative electrode
electrode sheet
Prior art date
Application number
PCT/CN2015/088136
Other languages
English (en)
Chinese (zh)
Inventor
田东
Original Assignee
田东
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 田东 filed Critical 田东
Publication of WO2016110111A1 publication Critical patent/WO2016110111A1/fr

Links

Images

Classifications

    • 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
    • H01M4/36—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
    • 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 method for preparing a negative electrode sheet for a lithium ion battery.
  • the negative electrode sheet according to the present invention uses a carbon fiber cloth.
  • Power battery refers to the battery used in electric vehicles, including lithium ion batteries, lead acid batteries, fuel cells, etc. Among them, lithium ion batteries have higher specific energy, higher specific power, less self-discharge, long service life and good safety. Other advantages have become the focus of current development in various countries.
  • the negative electrode material is one of the four major raw materials (positive electrode, negative electrode, electrolyte, and separator) of the lithium ion battery.
  • the commercial lithium ion battery anode material is made of graphite carbon material, which has a low lithium insertion/deintercalation potential and is suitable. It has the advantages of reversible capacity, abundant resources and low price, and is an ideal anode material for lithium ion batteries.
  • graphite is used as a negative electrode material, it is necessary to obtain a negative electrode sheet by a process of slurrying, coating, tableting, baking, etc., and then assembly with the positive electrode sheet and other subsequent work, and finally only a lithium ion finished product.
  • Carbon fiber has a wide range of applications and is a carbon material with excellent properties. It has many advantages such as high strength, small coefficient of thermal expansion, good thermal conductivity and excellent electrical conductivity.
  • Chinese patent CN 102623704A by adding carbon fiber, utilizes its high conductivity and strength. Adsorption to prepare lithium carbonate-carbon fiber composite anode materials to solve the problem of material large-rate charge and discharge performance and improve conductivity, to meet the requirements of modern society for lithium-ion battery applications.
  • Chinese patent CN 102290582A by adding nano-long carbon fiber VGCF, improves battery conductivity and reduces internal resistance.
  • a preparation method of a tin/graphene/carbon fiber composite lithium battery anode material disclosed in Chinese patent CN 104037393A a network structure composed of a mixture of graphene and carbon fiber, provides a large number of smooth transport channels for lithium ion in and out electrodes, so that it can be fully Contact with the anode material improves the utilization efficiency of the anode material. Improve the effective position of lithium storage in the negative electrode material and the transport speed of lithium during charge and discharge.
  • the high electrical conductivity of graphene and carbon fiber can quickly achieve carrier migration, improve output power and effectively reduce battery Internal resistance of the body.
  • Chinese patent CN 102560744A discloses a preparation method of general-purpose pitch-based carbon fiber, which successfully applies the spinning equipment of chemical fiber industry to the spinning production process of petroleum and coal-based isotropic spinnable asphalt, in the pre-oxidation process.
  • the gas phase oxidation method is adopted, and the pre-oxidation treatment is carried out by using the gas oxidant which is easy to operate and polluted.
  • an excellent process parameter optimization scheme is adopted, and the excellent production performance is successfully produced.
  • General purpose pitch based carbon fiber is adopted.
  • the invention is to provide a novel preparation method of a negative electrode sheet for a lithium ion battery, and to change a conventional method for obtaining a negative electrode sheet by using a graphite particle as a raw material, and finally obtaining a negative electrode sheet by a process of slurrying, coating, tableting, baking, and the like. It saves copper foil base, binder (CMC, SBR), conductive agent (SP) and other ingredients and accessories, as well as supporting production equipment.
  • the negative electrode sheet prepared by the invention combines the advantages of the carbon fiber, especially after the treatment by the graphitization step, further improves the conductivity and the gram capacity, and can meet the requirements of high rate charge and discharge.
  • a carbon fiber cloth is used as a preparation method of a negative electrode sheet for a lithium ion battery, and 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 carbon fiber spinnable asphalt is 150-300 ° C
  • the amount of residual carbon is ⁇ 60%
  • quinoline is not The solution (QI) ⁇ 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 heating rate is too high, which may cause the raw silk to melt, and the temperature is too low to achieve the effect of oxidation. If the temperature is too high, the carbonization treatment will be lowered. rate.
  • 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 size of the small piece is 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.
  • the negative electrode sheet prepared by the invention has better flexibility and toughness than the conventional negative electrode sheet because the whole negative electrode sheet is a whole, and the safety performance of the battery is improved;
  • the negative electrode sheet of the invention is intricately interlaced with carbon fiber filaments to form a good conductive network, and has excellent electrical conductivity, can greatly reduce the internal resistance of the final finished battery, and meet the requirements of large current charge and discharge of the lithium ion power battery;
  • the carbon fiber itself has more microporous structure, can ensure the absorption and retention of the electrolyte, meets the rapid ingress and egress of lithium ions, and has excellent cycle performance, and is an ideal anode material.
  • FIG. 1 is a schematic view showing the structure of a carbon fiber cloth negative electrode sheet of the present invention.
  • Figure 2 is a graph showing the charge and discharge curves of the negative electrode sheet of Example 1.
  • Figure 3 is a graph showing the rate discharge of the battery in Example 2.
  • 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 The air was heated to 230 ° C at a heating rate of 2 ° C / min, and oxidized for 12 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 140 ⁇ 3 ⁇ m.
  • the surface density was controlled at 31.3 ⁇ 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 130 ⁇ 3 ⁇ m and an areal density of 18.8 ⁇ 0.5 mg/cm 2 .
  • the carbon fiber was cut into a negative electrode piece having a length of 735 ⁇ 2 mm and a width of 57.5 ⁇ 0.1, and a nickel electrode was bonded to the end by a conductive adhesive.
  • the test was carried out by the half-cell test method.
  • the charge-discharge voltage is 0-2.0V, and the charge-discharge rate is 0.2C.
  • the battery performance can be tested.
  • the initial discharge capacity of the electrode material is 345.3mAh/g. See Figure 2, the first efficiency is 95.2%.
  • 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 with a flowing state, and the spinneret of the melt spinning machine is adjusted to receive a pitch fiber strand having a diameter of 5 ⁇ 1 ⁇ m, and the raw yarn is The air was heated to 200 ° C at a heating rate of 1.5 ° C / min, and oxidized for 10 hours.
  • the oxidized raw yarn was passed through a stripping and spinning fabric to obtain a pre-oxidized silk cloth, and the thickness was controlled at 105 ⁇ 3 ⁇ m.
  • the surface density was controlled at 23.5 ⁇ 0.5 mg/cm2, and the pre-oxidized wire cloth 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 98 ⁇ 3 ⁇ m and an areal density of 13.4 ⁇ 0.5 mg/cm 2 .
  • the carbon fiber was cut into a negative electrode piece having a length of 717 ⁇ 2 mm and a width of 57.5 ⁇ 0.1, and a nickel electrode was bonded to the end by a conductive adhesive.
  • the battery performance was tested by the half-cell method of Example 1, and the initial discharge capacity of the electrode material was 341.1 mAh/g, and the first efficiency was 94.2%.
  • 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.
  • the rate discharge curve is shown in Figure 3.
  • the test results are shown in Table 1.
  • Example 2 Using the artificial graphite in Comparative Example 1 as the negative electrode material, the same negative electrode tab which meets the requirements of the process in Example 2 was prepared. 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 use of the carbon fiber cloth of the present invention as the negative electrode sheet is lower in the specific capacity than the commercial negative electrode material, but the difference is not large. In terms of circulation, rate charging and discharging, and internal resistance of the battery, they all have stronger advantages than graphite particle-based anode materials.

Landscapes

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

Abstract

La présente invention concerne un procédé de fabrication d'un tissu en fibre de carbone utilisé en tant que feuille de cathode d'une batterie lithium-ion. Le procédé utilise une résine filable de fibre de carbone en tant que matière première, et comprend la préparation d'un précurseur, la préoxydation du précurseur, et la rupture par étirage, le filage et le tissage de celui-ci pour obtenir une fibre préoxydée, puis la conduite d'une carbonisation, une graphitisation, une coupe et un soudage d'une patte d'électrode sur celui-ci pour obtenir une feuille de cathode d'une batterie lithium-ion, où lesdits procédés de fabrication diffèrent totalement des procédés de fabrication actuels. La feuille de cathode fabriquée par le procédé modifie un procédé de fabrication conventionnel, et conserve des matériaux auxiliaires et l'utilisation de dispositifs de fabrication, de manière à réduire grandement les coûts de fabrication. Dans l'invention, des filaments de fibre de carbone tissés entrelacés forment un réseau électriquement conducteur avantageux ayant une bonne conductivité électrique, de manière à réduire grandement une résistance interne d'une batterie fabriquée, et répondre au besoin d'un courant élevé de la batterie lithium-ion lors de la charge et la décharge.
PCT/CN2015/088136 2015-01-08 2015-08-26 Procédé de fabrication de tissu en fibre de carbone utilisé en tant que feuille de cathode de batterie lithium-ion WO2016110111A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510007726.2 2015-01-08
CN201510007726.2A CN104538590B (zh) 2015-01-08 2015-01-08 一种碳纤维布用作锂离子电池负极片的制备方法

Publications (1)

Publication Number Publication Date
WO2016110111A1 true WO2016110111A1 (fr) 2016-07-14

Family

ID=52854086

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/088136 WO2016110111A1 (fr) 2015-01-08 2015-08-26 Procédé de fabrication de tissu en fibre de carbone utilisé en tant que feuille de cathode de batterie lithium-ion

Country Status (2)

Country Link
CN (1) CN104538590B (fr)
WO (1) WO2016110111A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538590B (zh) * 2015-01-08 2017-01-18 深圳市玖创科技有限公司 一种碳纤维布用作锂离子电池负极片的制备方法
CN105633346A (zh) * 2016-04-01 2016-06-01 中国科学技术大学 一种锂离子电池硅负极及其制备方法、锂离子电池
CN105826517A (zh) * 2016-06-13 2016-08-03 周虎 一种碳膜锂离子电池负极及生产方法
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN102713039A (zh) * 2010-01-21 2012-10-03 平松产业株式会社 碳纤维制无纺布、碳纤维、以及它们的制造方法、电极、电池、以及过滤器
CN103855361A (zh) * 2014-03-28 2014-06-11 清华大学 掺氮多孔碳纳米纤维布的制备方法
CN104538590A (zh) * 2015-01-08 2015-04-22 田东 一种碳纤维布用作锂离子电池负极片的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI279471B (en) * 2005-03-25 2007-04-21 Univ Feng Chia Method for manufacturing carbon fiber paper and construction thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102713039A (zh) * 2010-01-21 2012-10-03 平松产业株式会社 碳纤维制无纺布、碳纤维、以及它们的制造方法、电极、电池、以及过滤器
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
CN103855361A (zh) * 2014-03-28 2014-06-11 清华大学 掺氮多孔碳纳米纤维布的制备方法
CN104538590A (zh) * 2015-01-08 2015-04-22 田东 一种碳纤维布用作锂离子电池负极片的制备方法

Also Published As

Publication number Publication date
CN104538590B (zh) 2017-01-18
CN104538590A (zh) 2015-04-22

Similar Documents

Publication Publication Date Title
JP5334278B1 (ja) 炭素繊維材、炭素繊維材製造方法、前記炭素繊維材を有する材
WO2016110110A1 (fr) Procédé de préparation de pièce d'électrode négative de batterie au lithium-ion à composite silicium-carbone
CN107978732B (zh) 极片及电池
KR101478814B1 (ko) 서로 다른 크기의 활물질로 이루어진 복수의 코팅층을 갖는 전극 구조체 및 이를 포함하는 이차전지.
CN111435761B (zh) 一种全固态锂离子电池及其多层电解质膜热压制备的方法
CN103050704B (zh) 一种多孔导电添加剂及其制备方法、锂离子电池
WO2012163300A1 (fr) Batterie
CN104810504A (zh) 一种柔性石墨烯集流体与活性材料一体化电极极片及其制备方法
CN112670507B (zh) 金属硒化物负载的碳纳米纤维的锂硫电池中间层的制备方法及锂硫电池
WO2016110113A1 (fr) Procédé de préparation de feuille d'électrode négative de pile lithium-ion utilisant un tissu de fibres de carbone comme matrice
WO2016206548A1 (fr) Procédé de préparation de matériau d'électrode négative modifié haute tension pour pile au lithium
CN110364761B (zh) 一种高能量密度长循环磷酸铁锂电池
KR101209847B1 (ko) 다공성 ｃｎｆ 집전체 및 이를 이용한 전극과 그의 제조방법
CN112420984A (zh) 一种负极片和锂离子电池
CN111048749B (zh) 一种负极极片、锂离子电池及其制造方法
CN111799470B (zh) 正极极片及钠离子电池
WO2016110111A1 (fr) Procédé de fabrication de tissu en fibre de carbone utilisé en tant que feuille de cathode de batterie lithium-ion
CN108878893B (zh) 一种快充锂离子电池负极用改性集流体及其制备方法
CN111048738B (zh) 一种能够提高电池性能的电池极片的制备方法
CN103035925A (zh) 一种锂离子动力电池、锂离子动力电池集流体及负极极片
CN116995192A (zh) 一种补钠正极极片及其制备方法和钠离子电池
WO2016110112A1 (fr) Procédé de préparation de matériau d'anode de pile au lithium-ion
JP2011003795A (ja) 電極集電体及びその製造方法、電極並びに蓄電素子
US9705135B2 (en) Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery
CN101527370A (zh) 一种动力锂离子电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15876613

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 15876613

Country of ref document: EP

Kind code of ref document: A1