WO2016110112A1 - Procédé de préparation de matériau d'anode de pile au lithium-ion - Google Patents

Procédé de préparation de matériau d'anode de pile au lithium-ion Download PDF

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Publication number
WO2016110112A1
WO2016110112A1 PCT/CN2015/088143 CN2015088143W WO2016110112A1 WO 2016110112 A1 WO2016110112 A1 WO 2016110112A1 CN 2015088143 W CN2015088143 W CN 2015088143W WO 2016110112 A1 WO2016110112 A1 WO 2016110112A1
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WO
WIPO (PCT)
Prior art keywords
carbon fiber
lithium ion
ion battery
anode material
battery anode
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PCT/CN2015/088143
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English (en)
Chinese (zh)
Inventor
田东
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田东
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Publication of WO2016110112A1 publication Critical patent/WO2016110112A1/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
    • H01M4/36—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
    • 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 material for a lithium ion battery.
  • the negative electrode material of the present invention is formed by combining carbon fiber filaments and short wires of different length/diameter ratios at a certain ratio.
  • Lithium-ion batteries have rapidly occupied the civilian secondary battery market at an average annual rate of 15%, and have become the first choice for portable electronic devices. power supply.
  • the rapid development of lithium-ion batteries is mainly due to the contribution of electrode materials, especially the improvement of anode materials.
  • Lithium-ion battery anode materials are required to have the following characteristics: 1 as low as possible electrode potential; 2 ions have a higher diffusivity in the negative solid state structure; 3 height deintercalability; 4 good conductivity and thermodynamic stability; 5 good safety performance; 6 good compatibility with electrolyte solvent; 7 rich in resources, low in price, no pollution to the environment.
  • 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.
  • Carbon materials have been widely used in lithium ion batteries because of their low cost, non-toxicity and superior electrochemical properties. Its interface state and fine structure have a great influence on electrode performance.
  • commercial lithium-ion battery carbon anode materials can be divided into graphite, hard carbon and soft carbon. Among them, graphite materials are still the mainstream of lithium-ion battery anode materials.
  • the carbon anode materials currently studied mainly include graphite materials and low temperature pyrolytic carbon.
  • As a negative electrode material for lithium ion batteries carbon materials still have shortcomings such as low charge and discharge capacity, large irreversible loss of primary circulation, co-insertion of solvent molecules and high production cost. These are the key problems to be solved in the research of lithium ion batteries.
  • Carbon fiber has attracted great attention due to its high degree of crystal orientation, good electrical and thermal conductivity, and has been widely studied as a supercapacitor and lithium ion battery anode material, and has broad application prospects.
  • the electrochemical properties of lithium-ion battery carbon anode materials have a strong correlation with microscopic crystal structure and surface properties. Among them, the degree of graphitization of materials has a significant effect on material properties.
  • Carbon fiber is a new type of carbon material. According to raw materials, there are mainly PAN-based carbon fibers (more than 90% of the carbon fibers on the market), viscose-based carbon fibers, and pitch-based carbon fibers. In general, pitch-based carbon fibers have a lower electrical resistivity than PAN-based carbon fibers, and PAN-based carbon fibers have a higher electrical resistivity than viscose-based carbon fibers. small. The electron rate decreases as the heat treatment temperature increases.
  • Chinese patent CN 102623704A by adding carbon fiber, using its high conductivity and strong adsorption to prepare lithium carbonate-carbon fiber composite anode material to solve the problem of material large rate charge and discharge performance and improve conductivity, to meet the needs of modern society for lithium ion battery Requirements.
  • 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 the internal resistance of the battery itself.
  • 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.
  • Carbon fiber is generally a filament structure, and its application in the field of lithium ion batteries is mainly used as a conductive agent. If it is directly used as a negative electrode material, there are many difficulties in formulation, easy precipitation of the slurry, uneven coating density of the pole piece, poor appearance of the pole piece, and the like. problem.
  • the invention provides a novel lithium ion battery anode material, the purpose of which is to solve the application problem of carbon fiber in lithium ion battery and expand the application range thereof.
  • the technical problem solved by the present invention is achieved by the following technical solution, and a preparation method of a novel lithium ion battery anode material, the preparation steps are as follows:
  • Preparation of carbon fiber short yarn the carbon fiber after graphitization is pulverized to obtain a carbon fiber short yarn having a length of 20 to 50 ⁇ m and a length of: 1:0.4 to 0.8;
  • 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 temperature of the high temperature graphitization treatment is 2600 ° C or higher.
  • the pulverization in the step (5) is one or more of a mechanical pulverizer, a jet mill, and a grinder.
  • the slitting in the step (6) means one or more of a cutter and a microtome capable of controlling the slit length.
  • the obtained carbon fiber is close to graphite in material by carbonization and graphitization, and is structurally superior to graphite and can be used as a negative electrode material;
  • the carbon fiber itself has more microporous structure, can ensure the absorption and retention of the electrolyte, meet the rapid ingress and egress of lithium ions, and has excellent cycle performance, and is an ideal anode material;
  • 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 is heated to 260 ° C at a heating rate of 2 ° C / min, and oxidized for 4 hours.
  • the pre-oxidized raw silk is heated to 900 ° C at a heating rate of 10 ° C / min under an inert gas atmosphere, and maintained at a high temperature. 2 hours, then cooled to room temperature.
  • the carbonized raw yarn is further graphitized at a high temperature.
  • the graphitized carbon fibers were passed through slitting to obtain carbon fiber filaments having a length of 2 mm.
  • the NMP N-methylpyrrolidone
  • 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 355 mAh/g, and the capacity retention rate after 100 cycles is 98.1%.
  • the carbon fiber spinnable pitch having a softening point of 150 ° C is heated to 180 ° 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 5 ⁇ 1 ⁇ m, and the raw yarn is
  • the air was heated to 170 ° C at a heating rate of 1.5 ° C / min, and oxidized for 22 hours.
  • the pre-oxidized raw silk was heated to 850 ° C at a heating rate of 5 ° C / min under an inert gas atmosphere, and maintained at a high temperature. 1 hour, then cooled to room temperature.
  • the carbonized raw yarn is further graphitized at a high temperature.
  • the graphitized carbon fibers were passed through slitting to obtain carbon fiber filaments having a length of between 2.5 mm.
  • the carbon fiber short filament: carbon fiber filament 1:0.4 ratio, stirred and mixed uniformly, thereby obtaining the lithium ion battery anode material prepared in the present example.
  • Example 2 The performance of the negative electrode material of the lithium ion battery of Example 2 was examined and tested by the same detection method as in Example 1.
  • the initial discharge capacity of the motor material was 349 mAh/g, and the capacity retention rate after 100 cycles was 96.8%.
  • the carbon fiber spinnable pitch with a softening point of 200 ° C is heated to 230 ° C to melt into a liquid having a flowing state, and the spinneret of the melt spinning machine is adjusted to collect a pitch fiber strand having a diameter of 10 ⁇ 1 ⁇ m, and the raw yarn is
  • the air was heated to 220 ° C at a heating rate of 4 ° C / min, oxidized for 5 hours, and the pre-oxidized raw silk was heated to 950 ° C at a heating rate of 10 ° C / min under an inert gas atmosphere, and maintained at a high temperature. 3 hours, then cooled to room temperature.
  • the carbonized raw yarn is further graphitized at a high temperature.
  • the graphitized carbon fibers were passed through slitting to obtain carbon fiber filaments having a length of between 3 mm.
  • the carbon fiber short wire: carbon fiber filament 1:0.5 ratio, stirred and mixed uniformly, that is, the lithium ion battery anode material prepared in the present example was obtained.
  • the performance of the negative electrode material of the lithium ion battery of Example 3 was examined and tested by the same detection method as in Example 1.
  • the initial discharge capacity of the negative electrode material was 352 mAh/g, and the capacity retention after 100 cycles was 97.6%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de préparation de matériau d'anode de pile au lithium-ion, le procédé consistant : à combiner des filaments de fibres de carbone et des brins courts de fibres de carbone de différents rapports longueur/diamètre en une proportion précise. Du brai de houille en fibres filable est utilisé comme matière première, et après carbonisation et graphitisation, les fibres de carbone acquises sont supérieures au graphite en termes de structure. Étant donné que les fibres de carbone possèdent davantage de structures micro-poreuses, l'absorption et la retenue d'un électrolyte peuvent être garanties, et l'exigence d'entrée et de sortie rapides d'ions lithium peut être satisfaite, par conséquent, les fibres de carbone présentent une excellente efficacité de circulation. Étant donné que la taille des filaments de fibres de carbone et des brins courts de fibres de carbone est régulée et que la proportion entre eux est optimisée, le matériau d'anode préparé présente une excellente efficacité de traitement, un bon aspect dans une pièce d'électrode, et peut satisfaire l'exigence d'une application de production à grande échelle de piles au lithium-ion.
PCT/CN2015/088143 2015-01-08 2015-08-26 Procédé de préparation de matériau d'anode de pile au lithium-ion WO2016110112A1 (fr)

Applications Claiming Priority (2)

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CN201510007727.7 2015-01-08
CN201510007727.7A CN104485457B (zh) 2015-01-08 2015-01-08 一种新型锂离子电池负极材料的制备方法

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Cited By (1)

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CN114437557A (zh) * 2022-01-24 2022-05-06 中钢集团鞍山热能研究院有限公司 一种锂离子电池负极材料用高软化点包覆沥青的制备方法

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CN104485457B (zh) * 2015-01-08 2016-10-05 深圳市玖创科技有限公司 一种新型锂离子电池负极材料的制备方法
CN112750988B (zh) * 2019-10-29 2022-08-02 宝武碳业科技股份有限公司 一种液体包覆油组合物及其制备方法和用途
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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JP2003331834A (ja) * 2002-05-09 2003-11-21 Mitsubishi Gas Chem Co Inc 非水溶媒二次電池用炭素材料の製造法
CN1670991A (zh) * 2004-03-16 2005-09-21 中国科学院金属研究所 一种改性的锂离子电池负极材料、负极及电池
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Publication number Priority date Publication date Assignee Title
CN114437557A (zh) * 2022-01-24 2022-05-06 中钢集团鞍山热能研究院有限公司 一种锂离子电池负极材料用高软化点包覆沥青的制备方法

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