[go: up one dir, main page]

WO2014094424A1 - Matériau de cathode de batterie lithium-ion, méthode de préparation de celui-ci et batterie lithium-ion - Google Patents

Matériau de cathode de batterie lithium-ion, méthode de préparation de celui-ci et batterie lithium-ion Download PDF

Info

Publication number
WO2014094424A1
WO2014094424A1 PCT/CN2013/080085 CN2013080085W WO2014094424A1 WO 2014094424 A1 WO2014094424 A1 WO 2014094424A1 CN 2013080085 W CN2013080085 W CN 2013080085W WO 2014094424 A1 WO2014094424 A1 WO 2014094424A1
Authority
WO
WIPO (PCT)
Prior art keywords
ion battery
lithium
lithium ion
nitrite
negative electrode
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2013/080085
Other languages
English (en)
Chinese (zh)
Inventor
杨胜男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huawei Technologies Co Ltd
Original Assignee
Huawei Technologies Co Ltd
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 Huawei Technologies Co Ltd filed Critical Huawei Technologies Co Ltd
Publication of WO2014094424A1 publication Critical patent/WO2014094424A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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 rechargeable lithium ion battery, in particular to a negative electrode material with high capacity and stable circulation performance, a preparation method thereof and a lithium ion battery composed of the negative electrode material.
  • the current industry mainly adopts four methods of nanometering, thinning, compounding and designing multi-level special structure to modify it, but the effect is not ideal, or the preparation process is complicated, and it is difficult to realize commercialization. Or the introduction of a large amount of inactive materials greatly reduces the advantage of high capacity of materials that can be alloyed with lithium.
  • nanometering is an effective solution to solve the problem of large volume expansion and shrinkage of materials that can be alloyed with lithium.
  • the main reason is that when the particle size is reduced by 1/2, the volume is reduced by 1/8, which is undoubtedly exciting.
  • High-energy ball milling, laser, high-temperature calcination, sol-gel method, etc. are used to prepare nano-powders; gas-liquid-solid (VLS) growth, oxide-assisted growth, plasma activation, electrodeposition Method to prepare nanowires and nanotubes.
  • VLS gas-liquid-solid
  • the disadvantage is that reducing the dimension of the material does not fundamentally solve the problem of inherent volume expansion, shrinkage and poor conductivity of the material, and the effective size such as the particle size of the nanoparticle ⁇ 10 Nm is also difficult to achieve in the process of industrialization.
  • the high surface energy of the nanoparticles also induces a serious agglomeration between the materials, which ultimately leads to unsatisfactory battery performance.
  • the preparation of nanowires/nanotubes is costly, the production cycle is long, and the length of the nanowires is limited, which is difficult to be practical.
  • the film material has a large specific surface area, and thinning the material can effectively reduce the volume change generated in the vertical direction of the film, thereby improving the cycle stability of the material. Therefore, film materials generally have high specific capacity and good cycle performance.
  • the disadvantages are that the film materials are mainly prepared by chemical vapor deposition, magnetron sputtering, pulsed laser deposition, vacuum evaporation coating, etc., and the preparation process is complicated, the cost is high, and it is difficult to mass-produce rapidly, and the commercialization process Limited.
  • the large specific surface area of the film leads to an increase in side reactions and irreversible capacity.
  • the third technical solution mainly introducing an active or inactive buffer matrix with good conductivity and small volume effect by means of coating, doping, etc., to prepare a multi-phase composite anode material, thereby suppressing volume expansion of the lithium alloy anode material, Shrinkage, that is, using a "buffer skeleton" to compensate for the expansion of the material.
  • a material that can be alloyed with lithium-a non-metal composite system mainly a material that can be alloyed with lithium/carbon composite system
  • (2) a material-metal composite system that can be alloyed with lithium Two systems.
  • the disadvantage is that the material/metal alloy system which can be alloyed with lithium can improve the electrical conductivity of the material which can be alloyed with lithium, but there are still problems of particle cracking and pulverization, which limits its further development; it can be alloyed with lithium.
  • materials/carbon conventional carbon materials such as graphite and amorphous carbon
  • carbon generally occupies a large specific gravity, and the content of materials which can be alloyed with lithium is small, thus impairing the high capacity advantage of the material;
  • composite materials such as lithium alloyed materials/CNTs (Graphene), but they are not yet mature.
  • the technical problem to be solved by the invention is to provide a modified lithium ion battery anode material and a preparation method thereof, and the special structure of the anode material can not only relieve the volume expansion of the material which can be alloyed with lithium but also stably improve the overall conductivity of the material. Sex to overcome the shortcomings of the prior art.
  • the technical solution adopted to solve the technical problem of the present invention is to provide a negative electrode material for a lithium ion battery, which comprises a material which can be alloyed with lithium, a chemically bonded organic group, and a material which can be alloyed with lithium.
  • a carbonaceous material that is chemically bonded to the material that can be alloyed with lithium by the organic group, and the material that can be alloyed with lithium is selected from the group consisting of Si, Sn, and Ge. , Pb, Sb, Al, Zn, an element of nanoparticles, nanowires, nanotubes, nanofibers, nanofilm materials, or one or more of Si, Sn, Ge, Pb, Sb, Al, Zn elements Alloy composite.
  • the organic group has the formula -(CH 2 ) n —B—(CH 2 ) n — wherein 0 ⁇ n ⁇ 100, and B is an aliphatic, aromatic and heterocyclic group. One of them.
  • the carbon material is selected from one or more of graphene, graphene oxide, carbon nanotubes, and carbon nanofibers.
  • Another technical solution adopted to solve the technical problem of the present invention is to provide a method for preparing a negative electrode material for a lithium ion battery, comprising the following steps:
  • Step 1 Dissolve the graphene powder in deionized water and perform ultrasonic dispersion. After the dispersion is uniform, a concentrated hydrochloric acid solution in which p-phenylenediamine is dissolved is added dropwise to the graphene solution, and after the addition is completed, the solution is further added to the graphene solution. Adding sodium nitrite to carry out the reaction, and stirring uniformly to obtain a first mixed solution;
  • Step 2 The first mixed solution is subjected to suction filtration, and the filter residue obtained by suction filtration is washed with deionized water and absolute ethanol several times until the filtrate is colorless, and then the washed residue is dried to obtain a powder;
  • Step 3 adding the powder in the second step and the silicon powder purified by the HF or NH 4 F solution to the organic solvent, and then adding the organic ester, and reacting under stirring to obtain the second mixed solution;
  • Step 4 The second mixed solution is subjected to suction filtration, and washed with absolute ethanol until the filtrate is colorless, and then the reaction product after washing is dried to obtain a negative electrode material of the lithium ion battery.
  • Another technical solution adopted to solve the technical problem of the present invention is to provide a method for preparing a negative electrode material for a lithium ion battery, comprising the following steps:
  • Step 1 adding the graphene powder and the silicon powder purified by the HF or NH 4 F solution to an organic solvent to form a mixed solution and performing ultrasonic dispersion, and adding p-phenylenediamine to the mixed solution after the dispersion is uniform. Further adding an organic ester to carry out the reaction and stirring, and then obtaining a reaction product;
  • Step 2 The reaction product obtained in the first step is subjected to suction filtration, and washed with deionized water and absolute ethanol until the filtrate is colorless, and then the reaction product after the washing is dried to obtain a negative electrode material of the lithium ion battery.
  • Another technical solution adopted to solve the technical problem of the present invention is to provide a lithium ion battery including a positive electrode tab, a negative electrode tab, and an electrolyte, the negative pole tab containing the lithium ion described above
  • the negative electrode material prepared by the one-step organic chemical reaction or the two-step organic chemical reaction can not only alleviate the volume expansion and contraction of the material which can be alloyed with lithium, but also introduce the carbon material. Improve the overall electrical conductivity of the material; more importantly, the material that can be alloyed with lithium in the modified material prepared by the method compared with the material/carbon coated material which can be prepared by the conventional method. Bonding with the carbon material through the organic group, the strong bonding force of the chemical bond will ensure the overall stability of the material, reduce the occurrence of disconnection in the electron conduction network, and further improve the electrochemical performance of the material.
  • Figure 1 is a flow chart showing a method of preparing a negative electrode material for a lithium ion battery of the present invention.
  • FIG. 2 is a flow chart showing another preparation method of the anode material of the lithium ion battery of the present invention.
  • FIG. 3 is a schematic view showing the synthesis of a negative electrode material of a lithium ion battery of the present invention.
  • Fig. 4 is a graph showing the first three charge and discharge curves of the lithium ion battery composed of the negative electrode material prepared in the first embodiment.
  • Fig. 5 is a graph showing the cycle performance of a lithium ion battery composed of the negative electrode materials prepared in Example 1 and Example 2 at 0.2C.
  • the invention provides a negative electrode material of a novel modified high-capacity lithium ion battery, and the electrical conductivity and cycle stability of the negative electrode material are greatly improved.
  • the anode material of the lithium ion battery includes a material that can be alloyed with lithium, a chemically bonded organic group, and a carbon material that coats the material that can be alloyed with lithium, the carbon material and lithium The alloyed materials are chemically bonded together by the organic groups.
  • the material alloyable with lithium is selected from the group consisting of nanoparticles, nanowires, nanotubes, nanofibers, nanofilm materials of one element of Si, Sn, Ge, Pb, Sb, Al, Zn, or contains one An alloy complex of one or more of the above-mentioned elements;
  • the organic group is of the formula -(CH 2 ) n —B—(CH 2 ) n — wherein 0 ⁇ n ⁇ 100, B is aliphatic, aromatic One of a group and a heterocyclic group;
  • the carbon material is selected from one or more of graphene, graphene oxide, carbon nanotubes, and carbon nanofibers.
  • the invention also provides a method for preparing a negative electrode material of a lithium ion battery by a two-step organic chemical reaction, as shown in FIG. 1, which comprises the following steps:
  • Step S01 dissolving the graphene powder in deionized water and performing ultrasonic dispersion. After uniformly dispersing, the concentrated hydrochloric acid solution in which p-phenylenediamine is dissolved is added dropwise to the graphene solution, and after the addition is completed, the solution is further added to the graphene solution. Adding sodium nitrite to carry out the reaction, and stirring uniformly to obtain a first mixed solution;
  • Step S02 the first mixed solution is subjected to suction filtration, and the filter residue obtained by suction filtration is washed with deionized water and absolute ethanol several times until the filtrate is colorless, and then the washed residue is dried to obtain a powder;
  • Step S03 adding the powder in the step S02 and the silicon powder purified by the HF or NH 4 F solution to the organic solvent, and then adding the organic ester, and reacting under stirring to obtain the second mixed solution;
  • Step S04 the second mixed solution is subjected to suction filtration, and washed with absolute ethanol until the filtrate is colorless, and then the reaction product after washing is dried to obtain a negative electrode material of the lithium ion battery.
  • step S01 graphene oxide is first prepared by a modified Hummers method, and then reduced to obtain graphene.
  • the ultrasonic dispersion time is 0.5 to 2 hours, and the reaction time is 4 hours.
  • the drying condition is to dry in a vacuum oven at a temperature of 80 ° C for 8 to 24 hours.
  • the silicon powder has an average diameter of 100 nm
  • the organic solvent is acetonitrile, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, At least one of octane
  • the organic lipid is isoamyl nitrite, methyl nitrite, ethyl nitrite, n-propyl nitrite, isopropyl nitrite, butyl nitrite, n-nitrite At least one of an ester, isobutyl nitrite, t-butyl nitrite, tert-butyl nitrite, octyl nitrite, amyl nitrite, and nitrite.
  • the drying condition is to dry in a vacuum oven at a temperature of 80 ° C for 8 to 24 hours.
  • the invention further provides a method for preparing a negative electrode material of a lithium ion battery by a one-step organic chemical reaction, as shown in FIG. 2, which comprises the following steps:
  • Step S011 adding the graphene powder and the silicon powder treated by the HF or NH 4 F solution to an organic solvent to form a mixed solution and performing ultrasonic dispersion, and adding p-phenylenediamine to the mixed solution after the dispersion is uniform, and then Adding an organic ester to carry out the reaction and stirring, and then obtaining a reaction product;
  • Step S012 the reaction product obtained in the step S011 is subjected to suction filtration, and washed with deionized water and absolute ethanol until the filtrate is colorless, and then the reaction product after the washing is dried to obtain a negative electrode material of the lithium ion battery.
  • step S011 graphene oxide is first prepared by a modified Hummers method, and then reduced to obtain graphene.
  • the ultrasonic dispersion time is 0.5 to 2 hours.
  • the chemical reaction time is 6 to 20 hours.
  • the silicon powder has an average diameter of 100 nm.
  • the organic solvent is at least one of acetonitrile, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, and octane;
  • the organic lipid is nitrous acid Isoamyl ester, methyl nitrite, ethyl nitrite, n-propyl nitrite, isopropyl nitrite, butyl nitrite, n-butyl nitrite, isobutyl nitrite, t-butyl nitrite, sub At least one of tert-butyl nitrate, octyl nitrite, amyl nitrite, and nitrite.
  • the drying conditions are dried in a vacuum oven at a temperature of 80 ° C for 8 to 24 hours.
  • FIG. 3 is a schematic view showing the synthesis of a negative electrode material of a lithium ion battery of the present invention, wherein M is a material which can be alloyed with lithium.
  • Graphene oxide was first prepared by a modified Hummers method and then reduced.
  • the obtained graphene (Graphene) 2-8 mg at 40-120 Ultrasonic dispersion in mL deionized water for 0.5 ⁇ 2h.
  • After dispersing evenly add 20 ml of concentrated hydrochloric acid solution containing 2-6 mmol of p-phenylenediamine to the solution, and add 2-6 to the solution after the addition is completed.
  • Methyl nitrite the reaction time is about 4h, and the whole process is stirred.
  • the obtained product was suction filtered, washed with deionized water and absolute ethanol until the filtrate was colorless, and then the obtained washed product was dried in a vacuum oven at 80 ° C for 8 to 24 h Get a powder.
  • the silicon powder after the surface oxide layer is removed.
  • FIG. 4 shows that the anode material prepared in the first embodiment is first in the range of 0.6 to 0.09. A steep slope appeared between V, and a long lithium-plated platform appeared from 0.09 V.
  • the first lithium insertion capacity was 2337.6 mAh/g, and the delithiation process was 0.2 to 0.58.
  • There is a long delithium slope between V the first lithium removal capacity is 1519.2 mAh / g; the lithium-plated platform of the two discharge curves after the negative electrode material is slightly higher, about 0.28 Around V, the starting voltage may correspond to the lithium intercalation process of graphene.
  • the second charging curve of the material is not much different from the first time, and the potential platform is relatively close, but the lithium-plated platform of the third charging curve is relatively short.
  • the lithium ion battery containing the anode material prepared in the first embodiment and the second embodiment has good cycle stability, and the lithium ion battery 50 containing the anode material prepared in the first embodiment is 50.
  • the capacity remains at about 570. mAh/g, the capacity of the lithium ion battery containing the anode material prepared in Example 2 after 50 cycles of about 396 mAh/g, a stable platform appeared after 10 times.
  • the test data shows that the lithium ion battery containing the comparative negative electrode material has the worst cycle stability, and its first lithium removal capacity is 1530. mAh/g, the subsequent cycle capacity decays very quickly, and the capacity drops to 279 mAh/g after 20 cycles. It can be seen that the cycle stability of the lithium ion battery containing the modified anode material does increase greatly.
  • the negative electrode material prepared by the one-step organic chemical reaction or the two-step organic chemical reaction can not only alleviate the large volume expansion and contraction of the material which can be alloyed with lithium, but also introduce the carbon material to improve the overall conductivity of the material; More importantly, compared with the material/carbon coating material which can be prepared by the conventional method and can be alloyed with lithium, the modified material prepared by the method can pass between the material alloyed with lithium and the carbon material.
  • the organic group bonding, the strong bonding force of the chemical bond will ensure the overall stability of the material, reduce the occurrence of disconnection in the electron conduction network, and further improve the electrochemical performance of the material.

Landscapes

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

Abstract

L'invention concerne un matériau de cathode de batterie lithium-ion, comprenant un matériau capable de former un alliage avec le lithium, un groupe organique de liaison chimique, et un matériau carbone permettant de gainer le matériau capable de former un alliage avec le lithium ; et le matériau carbone est lié chimiquement au matériau capable de former un alliage avec le lithium par l'intermédiaire du groupe organique. L'invention concerne aussi une méthode de préparation du matériau de cathode de batterie lithium-ion. Le matériau de cathode évite non seulement l'expansion et la contraction considérables de volume du matériau capable de former un alliage avec le lithium, et le matériau carbone introduit facilite l'amélioration de la conductivité du matériau dans son ensemble ; de plus, le matériau de cathode assure aussi la stabilité générale du matériau de cathode, et réduit le risque de déconnexion de réseau pendant une transmission électronique, ce qui améliore davantage la performance électrochimique du matériau de cathode.
PCT/CN2013/080085 2012-12-20 2013-07-25 Matériau de cathode de batterie lithium-ion, méthode de préparation de celui-ci et batterie lithium-ion Ceased WO2014094424A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210556680.6 2012-12-20
CN201210556680.6A CN103887506A (zh) 2012-12-20 2012-12-20 锂离子电池的负极材料及其制备方法和锂离子电池

Publications (1)

Publication Number Publication Date
WO2014094424A1 true WO2014094424A1 (fr) 2014-06-26

Family

ID=50956307

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/080085 Ceased WO2014094424A1 (fr) 2012-12-20 2013-07-25 Matériau de cathode de batterie lithium-ion, méthode de préparation de celui-ci et batterie lithium-ion

Country Status (2)

Country Link
CN (1) CN103887506A (fr)
WO (1) WO2014094424A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104332601A (zh) * 2014-10-31 2015-02-04 天津大学 一步法制备钛基片/钛球形复合锂离子电池负极材料的方法
CN111943174A (zh) * 2020-07-26 2020-11-17 韩向斌 一种基于Li2O2嵌入石墨层制备石墨烯的方法
CN114804095A (zh) * 2022-04-27 2022-07-29 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用
CN114937766A (zh) * 2022-05-31 2022-08-23 济宁学院 过渡金属掺杂的聚间苯二胺包覆的正极材料的制备方法
CN118811798A (zh) * 2024-07-24 2024-10-22 湖北万润新能源科技股份有限公司 一种硬碳及其制备方法、负极极片和二次电池

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107180967A (zh) 2016-03-09 2017-09-19 东丽先端材料研究开发（中国）有限公司 一种石墨烯分散组成物、制备方法及锂离子电池电极浆料
CN108550817B (zh) * 2018-04-18 2021-08-10 北京化工大学 一种高性能锂离子电池铝基负极材料及其制备方法
CN110875470B (zh) * 2018-08-29 2021-04-06 天津大学 一种无定形锗基纳米线-石墨烯纳米复合锂离子电池负极材料及制备方法
CN114388791B (zh) * 2020-10-22 2023-07-14 山东海科创新研究院有限公司 一种用于锂离子电池的复合浆料、其制备方法及其应用
EP4507014A4 (fr) * 2022-04-26 2025-10-15 Songshan Lake Mat Lab Matériau d'électrode négative, plaque d'électrode négative et son procédé de préparation, et batterie au lithium-ion et son procédé de préparation
CN119634202B (zh) * 2025-02-14 2025-08-19 安徽大学 芳纶纳米纤维界面层修饰的锌金属材料及其作为水系锌离子电池负极材料的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142554A (zh) * 2011-02-16 2011-08-03 中国人民解放军63971部队 一种具有网络结构的纳米碳硫复合材料及其制备方法
CN102792498A (zh) * 2010-03-11 2012-11-21 株式会社Lg化学 聚合物-硅复合粒子、其制备方法以及包含所述聚合物-硅复合粒子的负极和锂二次电池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100553016C (zh) * 2004-08-26 2009-10-21 松下电器产业株式会社 电极用复合粒子及其制造方法以及二次电池
US20070224509A1 (en) * 2006-03-27 2007-09-27 Shin-Etsu Chemical Co., Ltd. SiCO-Li COMPOSITE, MAKING METHOD, AND NON-AQUEOUS ELECTROLYTE SECONDARY CELL NEGATIVE ELECTRODE MATERIAL

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102792498A (zh) * 2010-03-11 2012-11-21 株式会社Lg化学 聚合物-硅复合粒子、其制备方法以及包含所述聚合物-硅复合粒子的负极和锂二次电池
CN102142554A (zh) * 2011-02-16 2011-08-03 中国人民解放军63971部队 一种具有网络结构的纳米碳硫复合材料及其制备方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104332601A (zh) * 2014-10-31 2015-02-04 天津大学 一步法制备钛基片/钛球形复合锂离子电池负极材料的方法
CN104332601B (zh) * 2014-10-31 2016-10-19 天津大学 一步法制备钛基片/钛球形复合锂离子电池负极材料的方法
CN111943174A (zh) * 2020-07-26 2020-11-17 韩向斌 一种基于Li2O2嵌入石墨层制备石墨烯的方法
CN114804095A (zh) * 2022-04-27 2022-07-29 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用
CN114804095B (zh) * 2022-04-27 2023-12-12 中南大学 一种球化石墨微粉废料制得的石墨负极活性材料及制备方法和应用
CN114937766A (zh) * 2022-05-31 2022-08-23 济宁学院 过渡金属掺杂的聚间苯二胺包覆的正极材料的制备方法
CN114937766B (zh) * 2022-05-31 2023-10-31 济宁学院 过渡金属掺杂的聚间苯二胺包覆的正极材料的制备方法
CN118811798A (zh) * 2024-07-24 2024-10-22 湖北万润新能源科技股份有限公司 一种硬碳及其制备方法、负极极片和二次电池

Also Published As

Publication number Publication date
CN103887506A (zh) 2014-06-25

Similar Documents

Publication Publication Date Title
WO2014094424A1 (fr) Matériau de cathode de batterie lithium-ion, méthode de préparation de celui-ci et batterie lithium-ion
CN102569805B (zh) 储能复合粒子、电池负极材料以及电池
CN106848199B (zh) 一种锂离子电池纳米硅/多孔碳复合负极材料及其制备方法和应用
CN103078092B (zh) 一种制备锂离子电池硅碳复合负极材料的方法
CN107658452B (zh) 一种硅/碳纳米管/碳氧化硅复合材料及制备方法和应用
CN105489854B (zh) 一种高容量负极材料的制备方法
CN106099076B (zh) 一种花状氮掺杂碳包覆铋结构复合材料及其制备方法和应用
CN107946561A (zh) 负极材料及其制备方法、负极极片及锂离子电池
WO2015124049A1 (fr) Procédé de préparation de matériau d'électrode négative pour pile au lithium-ion
CN109167031A (zh) 一种纳米硅碳复合材料及其制备方法和应用
WO2013005887A1 (fr) Matière active de cathode utilisant un cœur-écorce de silicone-carbone pour une batterie secondaire au lithium et procédé de fabrication de ladite matière
CN106558683B (zh) 包覆型负极材料及其制备方法
CN105140464B (zh) 碳包氧化镍纳米片负载在石墨烯上的纳米复合材料及其制备方法
CN111816859A (zh) 硅基负极材料、其制备方法及锂离子二次电池
CN111769272A (zh) 一种Bi@C空心纳米球复合材料及其制备方法与应用
CN108448090A (zh) 一种锂电池硅碳复合负极材料的制备方法
WO2018161378A1 (fr) Nanoparticule de silicium à revêtement de graphène ayant une structure innovante et son procédé de préparation
CN118026181A (zh) 一种锂离子电池负极材料用硅碳纳米复合材料的感应热等离子体原位合成方法
CN108249428A (zh) 一种基于电解液溶剂热插锂剥离制备单层石墨烯的方法
CN108963237A (zh) 一种钠离子电池负极材料的制备方法
CN113097485B (zh) 一种类三明治结构SnSe/r-GO复合物及其制备方法和应用
CN112786871A (zh) 硅基负极材料及其制备方法、负极、电池和电子设备
CN113054170A (zh) 镍-镍钼氧化物-石墨烯复合材料的制备方法及其应用于锂离子电池
CN115911305B (zh) 一种锂离子电池负极材料及其制备方法
CN118315552A (zh) 一种原位碳包覆补锂的硅碳负极材料、制备方法及应用

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: 13865154

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13865154

Country of ref document: EP

Kind code of ref document: A1