CN112614997B - Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material - Google Patents

Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material Download PDF

Info

Publication number
CN112614997B
CN112614997B CN202011511193.9A CN202011511193A CN112614997B CN 112614997 B CN112614997 B CN 112614997B CN 202011511193 A CN202011511193 A CN 202011511193A CN 112614997 B CN112614997 B CN 112614997B
Authority
CN
China
Prior art keywords
hof
organic framework
hydrogen bond
carbon
carbon fluoride
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.)
Active
Application number
CN202011511193.9A
Other languages
Chinese (zh)
Other versions
CN112614997A (en
Inventor
候小鹏
李秀涛
曾浩
杜邵文
李娜
朱怡雯
傅小珂
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.)
Civil Aviation University of China
Original Assignee
Civil Aviation University of China
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 Civil Aviation University of China filed Critical Civil Aviation University of China
Priority to CN202011511193.9A priority Critical patent/CN112614997B/en
Publication of CN112614997A publication Critical patent/CN112614997A/en
Application granted granted Critical
Publication of CN112614997B publication Critical patent/CN112614997B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/58—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
    • H01M4/5835—Comprising fluorine or fluoride salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • 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

Abstract

The invention discloses a preparation method of a carbon fluoride anode material based on a hydrogen bond organic framework material. The porous carbon material containing the heteroatom is obtained by taking a porous material-hydrogen bond organic framework material as a raw material and carbonizing at high temperature, and the carbon fluoride anode material containing the heteroatom is obtained by fluorinating the porous carbon material under the heating condition by taking a mixed gas consisting of fluorine gas, hydrogen fluoride and argon as a fluorinated gas; because the porous carbon material contains a large amount of heteroatoms, and the heteroatoms can enable the generation of C-F bonds to be easier through the electron induction effect, the fluorination reaction temperature can be reduced, and the generated C-F bonds are mostly semi-ionic bonds, so that the discharge voltage platform of the carbon fluoride anode material can be improved; in addition, the method of the present invention uses a mixed gas of fluorine gas, hydrogen fluoride and argon gas as the fluorination gas, and the fluorination reaction temperature can be lowered to some extent due to the strong polarization effect of hydrogen fluoride.

Description

Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material
Technical Field
The invention belongs to the technical field of carbon material synthesis, and particularly relates to a preparation method of a carbon fluoride anode material based on a hydrogen bond organic framework material.
Background
Lithium/fluorocarbon batteries have the highest theoretical energy density among the existing primary batteries, and thus have been widely used in the fields of aerospace, military industry, medical treatment, and the like. At present, carbon fluoride materials have been reported mainly as: the battery using the fluorinated graphene and the fluorinated carbon nanotube as the anode material has more researches, and the material has larger specific capacity, but has the defect of lower discharge voltage platform, thereby influencing the specific energy of the whole fluorinated carbon battery. Meanwhile, the carbon source of the carbon fluoride material is graphene and carbon nano tubes, so that the cost of raw materials is high; and the fluorination conditions are harsh (fluorination at a temperature of more than 500 ℃ in a fluorine gas atmosphere), so that the method is not favorable for industrial production.
Metal organic framework Materials (MOFs) have been used for preparing carbon fluoride positive electrode materials (for example, patent patents: CN201910398470.0, CN201910415544.7, CN201910398454.1 and CN201910415216.7), although the performance of the carbon fluoride battery can be improved to a certain extent, the materials contain a large amount of metal elements, so that the production cost and the post-treatment cost are high, the materials are difficult to prepare carbon materials containing non-metal heteroatoms (such as boron, nitrogen and the like) in situ, and the carbon materials containing the non-metal heteroatoms have been proved to have the advantages of low fluorination temperature and good performance of the carbon fluoride battery.
Recently, hydrogen bonding organic framework materials (HOFs) constructed by self-assembly of small organic molecular monomers through hydrogen bonding, pi-pi stacking and van der waals interactions have been reported, and have gradually become an important branch of porous organic materials as a novel crystalline porous material by virtue of properties such as large specific surface area, high porosity, low density, high adsorptivity and the like. The material is mainly composed of light elements (C, H, O, N, B and the like), so the material is expected to become an important raw material source of the carbon fluoride material.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a carbon fluoride cathode material based on a hydrogen bond organic framework material.
In order to achieve the above object, the present invention provides a method for preparing a carbon fluoride cathode material based on a hydrogen bond organic framework material, comprising the following steps in sequence:
(1) carrying out high-temperature carbonization on the hydrogen bond organic framework material in a nitrogen atmosphere, and then cooling to room temperature to obtain a carbon fluoride precursor carbon source;
(2) and (2) placing the carbon fluoride precursor carbon source in a reaction kettle for drying, introducing a mixed gas consisting of fluorine gas, hydrogen fluoride and argon as a fluorinated gas for carrying out a fluorination reaction, and carrying out vacuum drying after the fluorination reaction is finished to obtain the carbon fluoride cathode material.
In the step (1), the hydrogen bond organic framework material is selected from at least one of 2, 4-diamino-1, 3, 5-triazine hydrogen bond organic framework materials HOF-1, HOF-2, HOF-3, HOF-4, HOF-5, HOF-6, carboxylic acid hydrogen bond organic framework materials HOF-TCPB, HOF-TCBP, HOF-11, HOF-14, HOF-100, amide hydrogen bond organic framework materials HOF-8 and TTBI.
In the step (1), the temperature rise rate of the high-temperature carbonization is 1-5 ℃/min, the carbonization temperature is 500-1200 ℃, and the carbonization time is 1-6 hours.
In the step (2), the mixed gas consists of 10-50% by volume of fluorine gas, 10-30% by volume of hydrogen fluoride and 20-80% by volume of argon gas; the fluorination reaction temperature is 100-350 ℃, and the fluorination reaction time is 2-6 hours.
The main technical principle of the preparation method of the carbon fluoride anode material based on the hydrogen bond organic framework material provided by the invention is as follows: taking a porous material-hydrogen bond organic framework material as a raw material, carbonizing at high temperature to obtain a porous carbon material containing heteroatoms, adopting a mixed gas consisting of fluorine gas, hydrogen fluoride and argon as a fluorinated gas, and fluorinating the porous carbon material under a heating condition to obtain a carbon fluoride anode material containing the heteroatoms; because the porous carbon material contains a large amount of heteroatoms, and the heteroatoms can enable the generation of C-F bonds to be easier through the electron induction effect, the fluorination reaction temperature can be reduced, and the generated C-F bonds are mostly semi-ionic bonds, so that the discharge voltage platform of the carbon fluoride anode material can be improved; in addition, the method of the present invention uses a mixed gas of fluorine gas, hydrogen fluoride and argon gas as the fluorination gas, and the fluorination reaction temperature can be lowered to some extent due to the strong polarization effect of hydrogen fluoride.
Compared with the prior art, the preparation method of the carbon fluoride anode material based on the hydrogen bond organic framework material has the following effects: (1) the raw material is of a porous structure, does not contain metal elements, is rich in non-metal heteroatoms, can effectively reduce the fluorination reaction temperature, and improves the discharge voltage and specific capacity of the carbon fluoride anode material; (2) the mixed gas of fluorine gas and hydrogen fluoride is used as the fluorinated gas, so that the fluorination efficiency can be further improved, and the fluorination temperature can be reduced; (3) the carbon fluoride material prepared by the invention has rich inner holes, high specific surface area and good battery performance, can be applied to the fields of lithium ion batteries and the like, and has good application prospect.
Drawings
FIG. 1 is a monomer molecular structure of a representative hydrogen bonding organic framework material.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1
The preparation method of the carbon fluoride cathode material based on the hydrogen bond organic framework material provided by the embodiment comprises the following steps in sequence:
(1) carrying out high-temperature carbonization on 1.0g of 2, 4-diamino-1, 3, 5-triazine hydrogen bond organic framework material HOF-1 in a nitrogen atmosphere at the temperature rise speed of 5 ℃/min, the carbonization temperature of 900 ℃ for 4 hours, and then cooling to room temperature to obtain a carbon fluoride precursor carbon source;
(2) and (2) placing the carbon fluoride precursor carbon source in a reaction kettle, drying at the temperature of 150 ℃, introducing a mixed gas consisting of 30 volume percent of fluorine gas, 15 volume percent of hydrogen fluoride and 55 volume percent of argon as a fluorinated gas, heating to 220 ℃, carrying out fluorination reaction for 4 hours, continuously introducing argon to remove the unreacted fluorinated gas after the fluorination reaction is finished, and then carrying out vacuum drying to obtain the carbon fluoride cathode material.
FIG. 1 is a monomer molecular structure of a representative hydrogen bonding organic framework material. The specific surface area of the carbon fluoride cathode material provided by the embodiment is 973m measured by a BET method2(ii)/g; the fluorine-carbon ratio of the carbon fluoride anode material is 0.88 measured by an element analysis method; the test of an electrochemical test method shows that the carbon fluoride anode material has the discharge median voltage of 3.09V and the discharge specific capacity of 853mAh/g under the condition of 0.05C multiplying power.
Example 2
The preparation method of the carbon fluoride cathode material based on the hydrogen bond organic framework material provided by the embodiment comprises the following steps which are sequentially carried out:
(1) 1.0g of carboxylic acid hydrogen bond organic framework material HOF-TCPB is carbonized at high temperature in nitrogen atmosphere, the heating rate is 5 ℃/min, the carbonization temperature is 900 ℃, the carbonization time is 4 hours, and then the carbon fluoride precursor carbon source is obtained after cooling to room temperature;
(2) and (2) placing the carbon fluoride precursor carbon source in a reaction kettle, drying at the temperature of 150 ℃, introducing a mixed gas consisting of 40 volume percent of fluorine gas, 15 volume percent of hydrogen fluoride and 45 volume percent of argon as a fluorinated gas, heating to 210 ℃, carrying out fluorination reaction for 4 hours, continuously introducing argon to remove unreacted fluorinated gas after the fluorination reaction is finished, and then carrying out vacuum drying to obtain the carbon fluoride cathode material.
The specific surface area of the carbon fluoride cathode material provided by the embodiment is 933m measured by a BET method2(iv) g; the fluorine-carbon ratio of the carbon fluoride anode material is 0.91 measured by an element analysis method; the test of an electrochemical test method shows that the carbon fluoride anode material has the discharge median voltage of 3.28V and the discharge specific capacity of 859mAh/g under the condition of 0.05C multiplying power.
Example 3
The preparation method of the carbon fluoride cathode material based on the hydrogen bond organic framework material provided by the embodiment comprises the following steps which are sequentially carried out:
(1) carrying out high-temperature carbonization on 1.0g of amide hydrogen bond organic framework material HOF-8 in a nitrogen atmosphere at the temperature rise speed of 5 ℃/min, the carbonization temperature of 900 ℃ for 4 hours, and then cooling to room temperature to obtain a carbon source of a carbon fluoride precursor;
(2) and (2) placing the carbon fluoride precursor carbon source into a reaction kettle, drying at the temperature of 150 ℃, introducing a mixed gas consisting of 55% by volume of fluorine gas, 15% by volume of hydrogen fluoride and 30% by volume of argon gas as a fluorinated gas, heating to 200 ℃, carrying out fluorination reaction for 4 hours, continuously introducing argon gas after the fluorination reaction is finished to remove the unreacted fluorinated gas, and carrying out vacuum drying to obtain the carbon fluoride cathode material.
The specific surface area of the carbon fluoride cathode material provided by the embodiment is 878m measured by a BET method2(ii)/g; the fluorine-carbon ratio of the carbon fluoride anode material is 0.90 measured by an element analysis method; the test of an electrochemical test method shows that the carbon fluoride anode material has the discharge median voltage of 3.12V and the discharge specific capacity of 837mAh/g under the condition of 0.05C multiplying power.

Claims (4)

1. A preparation method of a carbon fluoride anode material based on a hydrogen bond organic framework material is characterized by comprising the following steps: the preparation method comprises the following steps which are carried out in sequence:
(1) carrying out high-temperature carbonization on the hydrogen bond organic framework material in a nitrogen atmosphere, and then cooling to room temperature to obtain a carbon source of a carbon fluoride precursor;
(2) and (2) placing the carbon fluoride precursor carbon source in a reaction kettle for drying, introducing a mixed gas consisting of fluorine gas, hydrogen fluoride and argon as a fluorinated gas for carrying out a fluorination reaction, and carrying out vacuum drying after the fluorination reaction is finished to obtain the carbon fluoride cathode material.
2. The method for preparing a hydrogen bonding organic framework material based carbon fluoride anode material as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the hydrogen bond organic framework material is selected from at least one of 2, 4-diamino-1, 3, 5-triazine hydrogen bond organic framework materials HOF-1, HOF-2, HOF-3, HOF-4, HOF-5, HOF-6, carboxylic acid hydrogen bond organic framework materials HOF-TCPB, HOF-TCBP, HOF-11, HOF-14, HOF-100, amide hydrogen bond organic framework materials HOF-8 and TTBI.
3. The method for preparing a hydrogen bonding organic framework material based carbon fluoride anode material as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the temperature rise rate of the high-temperature carbonization is 1-5 ℃/min, the carbonization temperature is 500-1200 ℃, and the carbonization time is 1-6 hours.
4. The preparation method of the hydrogen bond organic framework material-based fluorinated carbon cathode material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (2), the mixed gas consists of 10-50% by volume of fluorine gas, 10-30% by volume of hydrogen fluoride and 20-80% by volume of argon gas; the fluorination reaction temperature is 100-350 ℃, and the fluorination reaction time is 2-6 hours.
CN202011511193.9A 2020-12-18 2020-12-18 Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material Active CN112614997B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011511193.9A CN112614997B (en) 2020-12-18 2020-12-18 Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011511193.9A CN112614997B (en) 2020-12-18 2020-12-18 Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material

Publications (2)

Publication Number Publication Date
CN112614997A CN112614997A (en) 2021-04-06
CN112614997B true CN112614997B (en) 2022-07-01

Family

ID=75243595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011511193.9A Active CN112614997B (en) 2020-12-18 2020-12-18 Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material

Country Status (1)

Country Link
CN (1) CN112614997B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08222551A (en) * 1995-02-17 1996-08-30 Sony Corp Plasma etching of silicon oxide based material layer
CN1161952A (en) * 1996-03-26 1997-10-15 昭和电工株式会社 Method for production of perfluorocarbon
WO2008100002A1 (en) * 2007-02-16 2008-08-21 Ls Mtron, Ltd. Anode active material for rechargeable lithium ion battery, method for preparing the same, and lithium ion battery manufactured using the same
CN102137834A (en) * 2008-08-29 2011-07-27 埃克森美孚化学专利公司 Offgas cleanup in olefin hydroformylation
CN103384656A (en) * 2010-12-21 2013-11-06 索尔维特殊聚合物意大利有限公司 Process for producing fluorinated organic compounds
JP2015099722A (en) * 2013-11-20 2015-05-28 日本化学工業株式会社 Positive electrode active material for lithium secondary battery, manufacturing method of the same, and lithium secondary battery
WO2017032445A1 (en) * 2015-08-26 2017-03-02 Merck Patent Gmbh Perfluorinated compounds with reactive groups
JP2017082274A (en) * 2015-10-27 2017-05-18 国立大学法人京都大学 Electrolysis unit for fluorine gas generation, fluorine gas generator and manufacturing method of fluorine gas
CN108390036A (en) * 2018-02-23 2018-08-10 成都新柯力化工科技有限公司 A kind of the lithium sulphur battery electrode material and preparation method of organic frame stabilization
JP2019110043A (en) * 2017-12-19 2019-07-04 トヨタ自動車株式会社 Battery system
CN110165210A (en) * 2019-05-14 2019-08-23 中国民航大学 A kind of preparation method of the fluorocarbons positive electrode with height ratio capacity

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08222551A (en) * 1995-02-17 1996-08-30 Sony Corp Plasma etching of silicon oxide based material layer
CN1161952A (en) * 1996-03-26 1997-10-15 昭和电工株式会社 Method for production of perfluorocarbon
WO2008100002A1 (en) * 2007-02-16 2008-08-21 Ls Mtron, Ltd. Anode active material for rechargeable lithium ion battery, method for preparing the same, and lithium ion battery manufactured using the same
CN102137834A (en) * 2008-08-29 2011-07-27 埃克森美孚化学专利公司 Offgas cleanup in olefin hydroformylation
CN103384656A (en) * 2010-12-21 2013-11-06 索尔维特殊聚合物意大利有限公司 Process for producing fluorinated organic compounds
JP2015099722A (en) * 2013-11-20 2015-05-28 日本化学工業株式会社 Positive electrode active material for lithium secondary battery, manufacturing method of the same, and lithium secondary battery
WO2017032445A1 (en) * 2015-08-26 2017-03-02 Merck Patent Gmbh Perfluorinated compounds with reactive groups
JP2017082274A (en) * 2015-10-27 2017-05-18 国立大学法人京都大学 Electrolysis unit for fluorine gas generation, fluorine gas generator and manufacturing method of fluorine gas
JP2019110043A (en) * 2017-12-19 2019-07-04 トヨタ自動車株式会社 Battery system
CN108390036A (en) * 2018-02-23 2018-08-10 成都新柯力化工科技有限公司 A kind of the lithium sulphur battery electrode material and preparation method of organic frame stabilization
CN110165210A (en) * 2019-05-14 2019-08-23 中国民航大学 A kind of preparation method of the fluorocarbons positive electrode with height ratio capacity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《Porous Hydrogen-bonded Organic Frameworks (HOFs): Status and Challenges》;Lin, ZJ等;《ACTA CHIMICA SINICA》;20201215;第78卷(第12期);全文 *

Also Published As

Publication number Publication date
CN112614997A (en) 2021-04-06

Similar Documents

Publication Publication Date Title
CN109148847B (en) Boron-doped modified hard carbon-coated negative electrode material with high rate performance and liquid-phase preparation method thereof
CN108807876B (en) Preparation method of modified carbon negative electrode material for lithium ion battery
CN111146424B (en) Metal sulfide/carbon composite material, and preparation method and application thereof
CN109167025B (en) Boron-doped modified soft carbon-coated negative electrode material with high stability in high and low temperature environments and preparation method thereof
CN110112394B (en) Preparation method of carbon fluoride/metal fluoride composite positive electrode material
CN110880599A (en) Preparation method of high-performance fluorinated peanut shell hard carbon electrode material
CN111293308B (en) Negative electrode material, negative electrode, potassium ion battery and preparation method
CN109148843B (en) Boron-doped negative electrode material with good high-temperature performance and solid-phase preparation method thereof
CN110752352B (en) Preparation method for carbon-coated silicon negative electrode material synthesized by aid of boron-nitrogen-doped polymer
Shi et al. Carbon nanotubes-enhanced lithium storage capacity of recovered silicon/carbon anodes produced from solar-grade silicon kerf scrap
CN110165210B (en) Preparation method of carbon fluoride anode material with high specific capacity
CN111082034B (en) Preparation of tin/tin phosphide/carbon composite material of alkali metal ion battery cathode
CN111276694A (en) Preparation method of polyimide derived carbon/molybdenum disulfide negative electrode material and application of polyimide derived carbon/molybdenum disulfide negative electrode material in potassium ion battery
CN112614997B (en) Preparation method of carbon fluoride anode material based on hydrogen bond organic framework material
CN110808177B (en) Preparation method and application of silkworm cocoon derived carbon/carbon nanotube/copper sulfide composite material
CN111969201A (en) Preparation method of fluorine-doped phenolic resin-based hard carbon negative electrode material
CN110127659B (en) Preparation method of carbon fluoride anode material with high discharge voltage platform
CN116741972A (en) Carbon-compounded mixed polyanion compound for sodium ion battery anode material and preparation method thereof
CN112351951A (en) Production method of nitrogen-doped graphene
CN106992294B (en) High-voltage lithium nickel manganese oxide positive electrode composite material, preparation method thereof and lithium ion battery
CN112607724A (en) Preparation method of carbon fluoride anode material based on covalent organic framework material
CN115472832A (en) Method for preparing high-capacity lithium battery negative electrode material from natural graphite spherical tailings
CN113130905A (en) Ultra-small cobalt sulfide nanosheet/carbon cloth composite material and preparation method thereof
Zhang et al. Hard Carbon Derived from Straw as Anode materials for sodium-ion batteries
CN115448289B (en) Oxygen-fluorine co-doped hard carbon anode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant