GB2619443A - Graphene-based nitride negative electrode material and preparation method therefor - Google Patents

Graphene-based nitride negative electrode material and preparation method therefor Download PDF

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GB2619443A
GB2619443A GB2313657.5A GB202313657A GB2619443A GB 2619443 A GB2619443 A GB 2619443A GB 202313657 A GB202313657 A GB 202313657A GB 2619443 A GB2619443 A GB 2619443A
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graphene
negative electrode
prepared
electrode material
salt solution
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Yu Haijun
Xie Yinghao
Li Aixia
Zhang Xuemei
Li Changdong
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/362—Composites
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • H—ELECTRICITY
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    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
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    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • 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
    • 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
    • H—ELECTRICITY
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    • 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
    • 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

Disclosed in the present invention is a graphene-based nitride negative electrode material. The general chemical formula of the graphene-based nitride negative electrode material is: graphene@M9Si12N22, wherein M is at least one of Ni and Co. The graphene-based nitride negative electrode material has good cycle stability and relatively high capacitance.

Description

GRAPHENE-BASED NITRIDE NEGATIVE ELECTRODE MATERIAL AND
PREPARATION METHOD THEREOF
HELD
[0001] The present disclosure belongs to the technical field. of negative electrode materials fire lithium batteries, and specifically relates to a graphene-based nitride negative electrode material and a preparation method thereof
BACKGROUND
[0002] Lithium-ion batteries have become a research hotspot due to their advantages of high specific capacity, high charge-discharge efficiency, good. cycle performance and low costs. The rapid development, of electronic products and new energy vehicles technology has put forward. higher requirements for lithium-ion batteries. As an important part of lithium-ion batteries, negative electrode materials affect the specific energy and cycle life of batteries, and have been the focus of the research on lithium-ion batteries. With the development of lithium-ion battery technology, the requirements for high capacity and small volume are getting higher. Therefore, it is urgent to develop new negative electrode materials with high capacity.
[0003] Carbon materials are most widely used negative electrode materials for lithium-ion batteries with good cycle performance. However, due to their low theoretical capacity (372 mAh/g) and low volumetric specific capacity, carbon negative electrode materials are difficult to meet the requirements for high battery capacity of various electronic products and electric vehicles. Therefore, there is an urgent need to develop new 'negative electrode materials for lithium-ion batteries with high specific capacity, high charge-discharge efficiency and good cycle stability. In recent years, some of the non-carbon-based materials have become one of the current research hotspots of negative electrode materials for lithium-ion batteries due to their high specific capacity especially volumetric specific capacity, low deintercalation potential of lithium and excellent safely performance.
[0004] Among various researched new non-carbon-based negative electrode materials, transition metal nitrides have attracted extensive attention of scholars due to their features such as low and flat charge-discharge potential platform and highly reversible reaction characteristies. Transition metal nitrides have been developed into a series of promising negative electrode materials. Their high melting point and excellent electrochemical inertness facilitate their stable operation as electrode materials in humid and corrosive environments. Similar to transition metal oxides, most transition metal nitrides present a large volume change during charge and discharge, resulting in agglomeration, pulverization, cracking and exfoliation of active ingredients with the cycling, which greatly reduces the performance of lithium-ion batteries. At present, the cycle stability of non-carbon-based negative electrode materials for lithium-ion batteries cannot be comparable with graphite materials, How to improve and enhance the electrochemical performance of such materials and make them more practical has become a hotspot and difficulties in the current research field of electrode materials,
SUMMARY
[0005] The present disclosure aims to solve at least one of the technical problems existing in the prior art, For this purpose, the present disclosure provides a graphene-based nitride negative electrode material and. a preparation method thereof, and the graphene-based nitride negative electrode material has excellent cycle stability and high capacity.
[0006] The above technical objective of the present disclosure is achieved by the following technical solutions: [0007] A graphene-based nitride negative electrode material having a general chemical formula of graphene@NbSit2N22, wherein M is selected from the group consisting of Ni, Co and a mixture thereof.
[0008] Preferably, the graphene in the graphene @ 9 ' N22 is.n-doped graphene, [0009] Another objective of the present disclosure is to provide a method for preparing the above-mentioned graphene-based nitride negative electrode material.
[0010] A method for preparing the above-mentioned graphene-based nitride egative electrode material, comprising steps of: [0011] (1) preparing a metal salt solution containing nickel ions andJor cobalt ions, an ammonium salt solution and a silicate solution, respectively; [0912] (2) mixing the ammonium salt solution prepared in step (1) with the metal salt solution prepared in step (1) to obtain a mixed solution; [0013] (3) dispersing graphene 1TM) the nixed. solutionprepared in step (2) to obtain a dispersion; [0014] (4) adding the dispersion prepared in step (3) to the silicate solution prepared in step (1) to obtain a suspension; [0015] (5) subjecting the suspension prepared in step (4) to a hydrothermal reaction to obtain a hydrothermal product, washing and drying the hydrothermal product to obtain a dry material; and [0016] (6) heating the dry material prepared in step (5) in an atmosphere containing ammonia followed by a constant temperature treatment, annealing, introducing an atmosphere of protective gas and cooling to room temperature to obtain the graphene-based nitride negative electrode material.
[0017] Preferably, the graphene in step (3) is graphene oxide.
[0918] Preferably, the metal salt solution in step (1) is selected from the group consisting of nickel chloride, nickel nitrate, cobalt chloride, cobalt nitrate and a mixture thereof, and a concentration of metal ions in the metal salt solution is 0.01-0.5 mon, [0019] Preferably, the ammonium salt solution in step (1) is selected from the group consisting of an ammonium chloride solution, an ammonium nitrate solution and a mixture thereof, and has 20 a concentration of 0.1-5 mono.
[0020] Preferably, the silicate solution in step (1) is a sodium silicate solution having a concentration of 0.1-1.0 molIL calculated as Si02.
[0021] Preferably, a molar ratio of metal ions to ammonium ions in the mixed solution prepared in step (2) is 1: (8-10).
[0922] Preferably, a. concentration of graphene in the dispersion prepared. in step (3) is 10,0-60.0 g/L, [0023] Preferably, in step (4), the adding comprises adding the dispersion to the silicate solution at a rate of 5-20 nil /min, and an amount ratio of the metal salt solution to the silicate solution is metal ions: Si-=3: 4.
[0024] Preferably, in step (5), the hydrothermal f the suspension is carried. out a temperature of 140"C-180°C. for 12-18 h. [0025] Preferably, in step (5), the drying comprises subjecting the hydrotherm p duct ts. vacuum drying at 120°C-150°C for 4-6 h. [0026] Preferably. in step (6), the constant temperature treatment is carried out at a temperature of 800°C-1300°C for 10-15 It [0027] Preferably, in step (6), the atmosphere is a mixed gas of ammonia and nitrogen in a volume ratio of 100: (0-20).
[0028] The beneficial effects of the present disclosure are as follows: [0029] (1) The graphene-based nitride negative electrode material of the present disclosure has excellent capacity and cycle stability. The battery with it as the negative electrode material has an initial charge-discharge capacity of 537 rrilkhig or more, and a capacity retention rate of 91.51% or more after 100 cycles of charge and discharge.
[9030] (2) In the method for preparing the graphene-based. nitride negative electrode material of the present disclosure, firstly, a metal salt solution of nickel/cobalt and a silicate solution are subjected to a hydrothermal reaction to generate nickel/cobalt silicate, which is adhered on graphene that is previously dispersed in the metal salt solution to obtain a hydrothermal product, Then the hydrothermal product is reduced at high temperature under ammonia to prepare a grapheme-based nitride composite material. In this process, on the one hand., adding an ammonium salt solution in advance suppresses the production of hydroxide and finally generates nickel/cobalt silicate nanoparticies, and the reaction equations include: 3M2++4Si032-± 1120=M3Si4012H2+20F1-, 011-+N114'=NH3.1120; on the other hand, dispersing 25 graphene in the metal salt solution can make graphene adsorb metal ions in advance and allow the generated nickel/cobalt silicate to adhere better in the subsequent hydrothermal reaction.
[0031.] (3) In the method for preparing the graphene-hased nitride negative electrode material of the present disclosure, when the hydrothermal product is reduced with ammonia. at high temperature, the temperature is controlled to be 800-1300'C, so that both the carbon in the graphene and ammonia serve to reduce, facilitating the combination of metal, silicon and nitrogen to generate a nitride, and the reaction equation includes: 3M3Si40121:124-22NE13=M9Sit2N22+36F120. Meanwhile, when the graphene used is graphene oxide, oxygen in the oxygen-containing functional group that is present on the graphene oxide will react with ammonia to generate nitrogen-containing graphene and water, thereby producing a nitrogen-doped graphene material, which can further improve the capacity of the material. In addition, the overall strength of the material can be further improved due to the production of a silicon nitride material, thereby reducing the pulverization of material and further improving the cycle performance of the material while improving the specific capacity of the material,
BRIEF DESCRIPTION OF DRAWINGS
[0032] FIG, 1 is an SEM image of the graphe based nitride negative electrode material in Example I of the present disclosure.
DETAILED DESCRIPTION
[0033] The present disclosure will be further described below in conjunction with specific examples:
Example I:
[0034] A graphene-based nitride negative electrode material has a general chemical formula of nitrogen-doped graphene@NisSit2N22, and the SEM image of the graphene-based nitride negative electrode material in Example I is shown in HG. 1.
[0035] The method for preparing the above-mentioned graphene-based nitride negative electrode material comprises steps of: [0036] (1) A nickel chloride solution with a metal ion concentration of 0.01 mol/L was prepared.
[0037] (2) An ammonium chloride solution with a concentration of 0,1 molt was prepared.
[0038] (3) The ammonium salt solution obtained in step (2) was added dropwise to the salt solution in step (I) at a volume ratio of 1:1 to obtain a mixed solution.
[0039] (4) Ciraphene oxide was ultrasonically dispersed. in the mixed solution to obtain a dispersion with a graphene oxide concentration of 10.0 g/L, and the ultrasonic dispersing was continued.
[0040] (5) A sodium silicate solution with a concentration of 0.1 mo (calculated as 2) was prepared.
[0041] (6) The dispersion prepared in step (4) was added to the sodium silicate solution at a rate of 20 miLlmin to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4, [0042] (7) The suspension was placed in a hydrothermal reactor to react at a constant temperature of 140°C for 18 h, and then cooled naturally to room temperature to obtain a hydrothermal product.
[0043] (8) The hydrothermal product was washed with purified water, and then dried under 15 vacuum at 120°C for 6 h to obtain a dry material.
[0044] (9) The dry material was heated to 800°C in an ammonia atmosphere for 15 h. [0045] (10) After the reaction in step (9), annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the graphene-based. nitride negative electrode material.
Example 2:
[0046] A graphene-based nitride negative electrode material has a general chemical formula of graphene@Co9Sit2N22.
[0047] The method for preparing the above-mentioned graphene-based nitride negative electrode material comprises steps of: [0048] (1) A cobalt chloride solution with a metal ion concentration of 0.1 mol/L was prepared.
[0049] (2) An ammonium chloride solution with a concentration of 1.0 mol/L was prepared. [0(150] (3) The ammonium alt solution obtained in step (2) was added dropwise to the metal salt solution in step (1) at a volume ratio of 1:1 to obtain a mixed solution.
[0051] (4) Oraphene was ultrasonically dispersed in the mixed solution to obtain a dispersion with a graphene concentration of 60.0 giL, and the ultrasonic dispersing was continued..
[0052] (5) A sodium silicate solution with a concentration of 0.5 molls. (calculated as 2) was prepared.
[0053] (6) The dispersion prepared in step (4) was added to the sodium silicate solution at a rate of 10 miLimin to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4.
[0054] (7) The suspension was placed in a hydrothermal reactor to react at a constant 10 temperature of 160°C for 15.0 h., and then cooled naturally to room temperature to obtain a hydrothermal product.
[0055] (8) The hydrothermal product was washed with purified water, and then dried under vacuum at 130°C for 5 b to obtain a dry material.
[0056] (9) The dry material was heated to 1000°C in a mixed gas atmosphere for 12 h, and the mixed gas is a mixture of ammonia and nitrogen at a volume ratio of 100:10.
[0057] (10) After the reaction in step (9), annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the graphene-based nitride negative electrode material,
Example 3:
[0058] A graphene-b d nitride negative electrode material has a general chemical formula of graphene@Ni9Sit2N22.
[0059] The method for preparing the above-mentioned graphene-based nitride negative electrode material comprises steps of: [0060] (1) A nickel nitrate solution with a metal ion concentration of 0.5 molfL was prepared. 25 [0061] (2) An ammonium nitrate solution with a concentration of 0.1 moliL was prepared.
[0062] (3) The ammonium salt solution obtained in step (2) was added dropwise to the metal salt solution in step (1) at a volume ratio of 1:40 to obtain a mixed solution.
[0063] (4) Graphene was ultrasonically dispersed in the mixed solution to obtain a dispersion with a graphene concentration of 10.0 and the ultrasonic dispersing was continued.
[0064] (5) A sodium silicate solution with a concentration of 1.0 mon (calculated as 8102) was prepared..
[0065] (6) The dispersion prepared in step (4) was added to the sodium silicate solution at a rate of 5 mL/min to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4.
[0066] (7) The suspension was placed in a hydrothermal reactor to react at a constant temperature of 180°C for 18.0 h, and then cooled naturally to room temperature to obtain a hydrothermal product.
[0067] (8) The hydrothermal product was washed with pi ified water, and then dried under vacuum at 150°C for 4 h to obtain a dry material.
[0068] (9) The thy material was heated to 1300°C in a mixed gas atmosphere for h, and the mixed gas is a mixture of ammonia and nitrogen at a volume ratio of 100:20.
[0069] (10) After the reaction in step (9), annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the graphene-based nitride negative electrode material.
Comparative Example 1: [0070] A method for preparing a negative electrode material comprises steps of: [0071] (1) A nickel chloride solution with a metal ion concentration of 0.01 mon was prepared.
[0072] (2) Pure water was added dropwise to the metal salt solution step (1' at a volume ratio of 1:1 to obtain a mixed solution.
[0073] (3) Graphene oxide was ultrasonically dispersed in the mixed solution to obtain a dispersion with a graphene oxide concentration of 10,0 g/L, and the ultrasonic dispersing was continued.
[0074] (4) A sodium silicate solution with a concentration of 0.1 mon (calculated as 8102) was prepared.
[9975] (5) The dispersion prepared in step (3) was added to the sodium silicate solution at a rate of 20 mlimin to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4.
[0076] (6) The suspension was placed in a hydrothermal reactor to react at a constant temperature of 140°C for 18 h, and then cooled naturally to room temperature to obtain a hydrothermal product.
[0077] (7) The hydrothermal product was washed with purified water, and then dried under vacuum at 120C for 6 h to obtain a dry material.
[0078] (8) The dry material was heated to 800°C in an ammonia atmosphere for 15 h. [0179] (9) After the reaction in step (8), annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the net athe electrode material.
Comparative Example 2: [0(1801 A method for preparing a negative electrode material comprises steps of: [0081] (1) A cobalt chloride solution with a metal ion concentration of 0.1 mol/L was prepared.
[9982] (2) Pure water was added dropwise to the metal salt solution in step (1) at a volume ratio of 1:1 to obtain a mixed solution.
[0083] (3) Graphene was ultrasonically dispersed in the mixed solution to obtain a dispersion with a grapheme concentration of 60.0 g/L, and the ultrasonic dispersing was continued.
[09841 (4) A sodium silicate solution with a concentration of 0.5 molfL (calculated as Sith) was prepared.
[0085j (5) The dispersion prepared in step (3) was added to the sodium silicate solution at a rate of 10 miL/min to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4.
[0086] (6) The suspension was placed in a hydrothermal reactor to react at a constant temperature of 160°C for 15.0 h, and then cooled naturally to Morn temperature to obtain a hydrothermal product.
[0087] (7) The hydrothermal product was washed with purified and then dried under vacuum at 130°C for 5 h to obtain a dry material.
[0088] (8) The dry material was heated to 1000°C in a mixed. gas atmosphe d gas is a mixture of ammonia and nitrogen at a volume ratio of 100:10. t2. h, and [0089] (9) After the reaction in step (8), annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the negative electrode material.
Comparative Example 3: [0090] A method for preparing a negative electrode material comprises steps of: [0991] (1) A nickel nitrate solution al ion concentration of 0.5 mol/L was prepared.
[0092] (2) Pure water was added dropwise to the instal salt solution iii step (1) at a volume ratio of 1:40 to obtain a mixed solution.
[0093] (3) Grapherie was ultrasonically dispersed in the mixed solution to obtain a dispersion with a graphene concentration of 10.0 got, and the ultrasonic dispersing was continued.
[0094] (4) A sodium silicate solution with a concentration of 1.0 mol/L (calculated as Si(h) was prepared.
[0095] (5) The dispersion prepared in step (3) was added to the sodium silicate satin rate of 5 mUmin to obtain a suspension, and the amount ratio of the metal salt solution to the silicate solution was metal ions: Si=3: 4.
[0096] (6) The suspension was placed in a hydrothermal reactor to react at a constant temperature of 180°C for 18.0 h, and then cooled naturally to room temperature to obtain a hydrothermal product.
[0097] (7) The hydrothermal product was washed with purified water, and then dried under vacuum at 150C for 4 h to obtain a dry material.
[0098] (8) The dry material was heated to 1300°C in a mixed gas atmosphere for 10 and the mixed gas is a mixture of ammonia and nitrogen at a volume ratio of 100:20. - [0099] (9) After the reaction in step annealing was performed. Then the reaction system was introduced with nitrogen and cooled to room temperature to obtain the negative electrode material.
lest Example:
[00100] The negative electrode materials obtained in Examples 1-3 and Comparative Examples 1-3 were mixed with a conductive agent (SP) and a binder (CMC/SBR) and stirred uniformly to prepare an electrode slurry. The copper foil current collector with a thickness of 9 pm was coated with the slurry uniformly, dried under vacuum at 105°C for 12 h, and then cut to obtain a negative electrode sheet. A 2032 button cell was assembled in a glove box filled with high-purity argon, and tested for the charge and discharge performance at a temperature of 25°C with a. charge and discharge cut-off voltage of 5 inV-1.5 V. The test results are shown in Table 1: Table 1: Test results of performance Example 1 Initial Initial Capacity after charge-discharge Coulombic 1.00 cycles of.
capacity efficiency Capacity mAh/g 95% charge and 766 retention rate discharge inAhig 701 91.51%
Example 2 602 96%
558 92.69 % Example 3 537 97% 501 93.30% Comparative 634 87% 528 8128%
Example 1
Comparative 480 Example 2 399 83.12% 90% Comparative 411 92% 355 86.37% _..... . .... _____ [00101] As can be seen from Table 1., the batteries prepared from the graphene-based nitride negative electrode materials of the present disclosure had an initial charge-discharge capacity of 537 mAh/g or more, an initial Coulotnbic efficiency of 95% or mote, and the capacity retention rate of 9151% or more after 100 cycles of charge and discharge, indicating that the grapheme.-based nitride negative electrode material had excellent cycle stability and high capacity.
[09102] In addition, comparisons were performed between Example 1 and Comparative Example le between Example 2 and Comparative Example 2, and between Example 3 and Comparative Example 3, respectively. in the case that the ammonium salt solution was replaced with purified water without changing other conditions in the preparation process, the electrochemical performance of the obtained graphene-based nitride negative electrode material was significantly reduced.
[00103] The above-mentioned examples are preferred embodiments of the present disclosure. However, the embodiments of the present disclosure are not limited by the above-mentioned examples. Any other changes, modifications, substitutions, combinations, and simplification made without departing from the spirit and principle of the present disclosure should be deemed as equivalents and are all included in the protection scope of the present disclosure.

Claims (10)

  2. I. A graphene-based nitride neg of graphene@M9SinN22, wherein N mixture thereof. ode material having a general chemical formula d from the group consisting of N. Co and a 2. The graphene-based nitride negative electrode material according to claim 1, wherein the graphene in the graphene@NI9Sit2N22 is nitrogen-doped. graphene.
  3. 3. A method for preparing the graphene-based nitride egative electrode material according to claim 1 or 2, comprising steps of: (1) preparing a metal salt solution g ickel ions anclior cobalt on, iurn salt solution and a silicate solution, respectively; (2) mixing the ammonium salt solution prepared in step (1) with the metal salt solution prepared in step (I) to obtain a mixed solution; (3) dispersing graphene into the mixed solution prepared in step (2) to obtain a dispersion; (4) adding the dispersion prepared in step (3) to the silicate solution prepared in step (1) to obtain a suspension; (5) subjecting the suspension prepared in step (4) to a hydrothermal reaction to obtain a 20 hydrothermal product, washing and drying the hydrothermal product to obtain a dry material; and (6) heating the dry material prepared in step (5) in. an atmosphere containing ammonia followed by a constant temperature treatment, annealing, introducing an atmosphere of protective gas and cooling to room temperature to obtain the graphene-based nitride negative electrode material.
  4. 4. The method according to claim 3, wherein the graphene in step (3) is graphene oxide.
  5. 5. The method according to claim 3, wherein the metal salt solution in step (1) is selected from the group consisting of nickel chloride, nickel nitrate, cobalt chloride, cobalt nitrate and a mixture thereof, and a concentration of metal ions in the metal salt solution is 0.91-0.5 mol/L.
  6. 6. The method for preparing the graphene-based nitride negative electrode material according to claim 3, wherein a molar ratio of metal ions to ammonium ions in the mixed. solution prepared in step (2) is 1: (8-10).
  7. 7. The method according to claim 3, wherein a concentration of graphene in the dispersion prepared in step (3) is 10.0-60.0 giL.
  8. 8. The method according to claim 3, wherein in step (4), the adding comprises adding the dispersion to the silicate solution at a rate of 5-20 mLimin, and an amount ratio of the metal salt solution to the silicate solution is metal ions: Si=3: 4.
  9. 9. The method according to claim eren step (5), the hydrothermal reaction of the suspension is carried out at a temperature of 140'C-180°C for 12-18 it.
  10. 10. The method according to claim 3, wherein step (6), the constant temperature treatment is carried out at a temperature of 800'C-1.300'C for 10-15 It
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