CN116314772A - Graphite composite negative electrode material, preparation method thereof, negative electrode piece and lithium battery - Google Patents
Graphite composite negative electrode material, preparation method thereof, negative electrode piece and lithium battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 132
- 239000010439 graphite Substances 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 13
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Images
Classifications
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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
-
- 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
- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
-
- 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
The application relates to the field of lithium ion batteries, and discloses a graphite composite negative electrode material, a preparation method thereof, a negative electrode plate and a lithium battery. The graphite composite anode material is doped with metals generated by thermal decomposition of copper fluoride and metal nitride and non-decomposed metal nitride on the surface and/or inside of graphite. According to the preparation method, the graphite is doped with a plurality of metals at the molecular level through the thermal decomposition reaction, so that metal atoms are distributed more uniformly on the graphite, the synergistic effect among the metals is fully exerted, the advantages of good graphite circulation performance and high specific surface area are reserved, the impedance of the graphite is reduced through the doping of the metal, and the conductivity of the graphite cathode material is improved. In addition, the trace of undecomposed nitride doping can improve and promote the electrochemical performance of graphite, and ensure the full utilization of nitride. The whole preparation method avoids complicated operation steps, does not need expensive machine equipment, and fully saves labor cost and material cost.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a graphite composite negative electrode material and a preparation method thereof, a negative electrode plate and a lithium battery.
Background
With the continuous progress of society, the requirements of energy storage, electric automobiles, portable electronic equipment electric tools and the like on batteries are increasing. The negative electrode material is used as an important component of the battery, and has particularly obvious influence on the overall performance of the battery. The graphite electrode material has the advantages of low charge-discharge voltage platform, low cost, good safety and the like, and is a main negative electrode material of the current ion battery. However, the anisotropic structure of graphite limits the diffusion of metal ions in the graphite structure, and the selective incorporation of other non-carbon elements into the graphite negative electrode material can effectively alter the intercalation behavior of ions in the graphite electrode. Doping metallic elements into graphite materials can effectively improve its loading capacity, increase current density, and accelerate charge transport.
The existing metal element doping process is complicated in multiple steps, for example, in the modification of natural graphite anode materials by metal element ion doping (Li Jianjun and the like, the tenth national electrochemical conference treatise on the classification, 1999), graphite is required to be subjected to liquid-phase oxidation or chlorination treatment, then is immersed in a metal ion solution for treatment, and then is subjected to heat treatment at the temperature of more than 800 ℃, and the process has the advantages that the doped metal is unevenly distributed, the performance of the anode materials is influenced, the energy consumption is higher, the required equipment is more, the electrochemical performance of the anode materials is not obviously improved, and meanwhile, the obtained anode materials also need washing and drying treatment.
Disclosure of Invention
In view of the above, an object of the present application is to provide a graphite composite anode material, which enables the first efficiency of a battery to be improved;
another object of the present application is to provide a graphite composite anode material, so that the graphite composite anode material can improve the cycle performance of a battery;
another object of the present application is to provide a graphite composite anode material, so that the graphite composite anode material can improve the rate capability of a battery;
another object of the present application is to provide a method for preparing the graphite composite negative electrode material, so that the preparation method can perform metal doping on graphite at a molecular level, so that metal atoms are distributed more uniformly on the graphite, and meanwhile, the process steps are simpler and more convenient, and the energy consumption is lower;
another object of the present application is to provide a negative electrode tab and a lithium battery based on the above negative electrode material.
In order to solve or at least partially solve the above technical problems, as a first aspect of the present application, there is provided a graphite composite anode material doped with a metal generated by thermal decomposition of copper fluoride and a metal nitride and an undecomposed metal nitride on the surface and/or inside of graphite; the metal nitride is selected from Ni 3 N 2 、Zn 3 N 2 、Fe 6 N 2 One or two or more of them.
Optionally, the molar ratio of copper fluoride to metal nitride is 10 (1-10).
Optionally, the ratio of graphite to copper fluoride is 100g (0.05-0.15 mol).
Optionally, the thermal decomposition environment is between 100 and 650 ℃.
As a second aspect of the present application, there is provided a method for preparing the graphite composite anode material, including:
heating a mixture of graphite, copper fluoride and metal nitride in an ammonia atmosphere to convert the copper fluoride into copper nitride;
and changing the ammonia gas atmosphere into a protective gas or reducing gas atmosphere, and continuously heating the mixture to decompose copper nitride and metal nitride to enable metal to be attached to the surface and/or the inside of graphite, so as to obtain the graphite composite anode material which can be directly used without cleaning.
Optionally, the heating treatment temperature in the ammonia atmosphere is 280-350 ℃.
Optionally, the heat treatment temperature in the protective gas or reducing gas atmosphere is 400-650 ℃.
Optionally, the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide, methane and sulfur monoxide.
As a third aspect of the present application, there is provided a negative electrode sheet having the graphite composite negative electrode material described herein or the graphite composite negative electrode material prepared by the preparation method described herein as an active material.
As a fourth aspect of the present application, a lithium battery includes a positive electrode tab, a separator, an electrolyte, and a negative electrode tab as described herein.
Compared with the conventional metal doped graphite process, the method has at least the following outstanding beneficial effects:
1. the graphite is doped at the molecular level through thermal decomposition reaction, so that the metal atoms are uniformly distributed on the graphite. On one hand, the advantages of good graphite circulation performance and high specific surface area are maintained, and on the other hand, the impedance of graphite is reduced by doping metal, so that the conductivity of the graphite anode material is improved;
2. the specific capacity of the nitride which is not completely decomposed is higher than that of the graphite, and the electrochemical performance of the graphite can be improved and promoted by the trace nitride doping, so that the 100% utilization of the nitride is ensured;
3. the variables of the preparation process are time and temperature, so that complicated operation steps are avoided. The whole test process only needs a tube furnace, expensive machine equipment is not needed, and labor cost and material cost are fully saved;
4. the graphite is doped with a plurality of metals, so that the synergistic effect among the metals is fully exerted, and the conductivity of the graphite is improved;
5. the temperature required in the whole preparation process is not high, different nitrides are decomposed into metals in the heating process, the heat energy in the heating process is fully utilized, the energy waste is further reduced, and the used gases are environment-friendly gases, so that the environmental pollution can be reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application;
fig. 1 is an SEM image of a graphite composite anode material described herein.
Detailed Description
The application discloses a graphite composite anode material, a preparation method thereof, an anode piece and a lithium battery, and the technical parameters can be properly improved by a person skilled in the art by referring to the content of the application. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included herein. The products, processes and applications described herein have been described in terms of preferred embodiments, and it will be apparent to those skilled in the relevant art that variations and suitable modifications and combinations of the methods described herein can be made to practice and use the technology of the present application without departing from the spirit and scope of the present application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
It should be noted that, in this document, relational terms such as "first" and "second," "step 1" and "step 2," and "(1)" and "(2)" and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Meanwhile, the embodiments and features in the embodiments in the present application may be combined with each other without conflict.
The graphite composite anode material is prepared by uniformly doping metal by a thermal decomposition method. By bringing CuF under heating 2 、Ni 3 N 2 、Zn 3 N 2 、Fe 6 N 2 The reduction decomposition makes the graphite uniformly distributed on the surface and inside of the graphite, thereby improving various electrochemical properties of the graphite.
The graphite composite negative electrode material has good conductivity, the conductivity is larger than that of a single graphite electrode material, the cycling stability is good, the maximum capacity loss after cycling for 500 weeks is only 4.7%, the first efficiency is larger than 98.9%, and the specific capacity is more than 365 mAh/g.
In a first aspect of the present application, there is provided a graphite composite anode material doped with a metal generated by thermal decomposition of copper fluoride and a metal nitride and an undegraded metal nitride on the surface and/or inside of graphite; the metal nitride is selected from Ni 3 N 2 、Zn 3 N 2 、Fe 6 N 2 One or more of them, the SEM image of which is shown in FIG. 1.
In certain embodiments of the present application, the molar ratio of copper fluoride to metal nitride is 10 (1-10); in other embodiments of the present application, the molar ratio of copper fluoride to metal nitride is 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, or 10:10.
In certain embodiments of the present application, the ratio of graphite to copper fluoride is 100g (0.05 to 0.15 mol); in certain embodiments of the present application, the ratio of graphite to copper fluoride is 100g:0.05mol, 100g:0.06mol, 100g:0.07mol, 100g:0.08mol, 100g:0.09mol, 100g:0.10mol, 100g:0.11mol, 100g:0.12mol, 100g:0.13mol, 100g:0.14mol or 100g:0.15mol.
In certain embodiments of the present application, the thermal decomposition environment is 120-650 ℃; in certain embodiments of the present application, the thermal decomposition is carried out by heat treatment at 120-650 ℃ for 2-12 hours; in other embodiments of the present application, the thermal decomposition temperature may be 200-600 ℃, 250-400 ℃, 120-350 ℃, 280-350 ℃, 400-650 ℃, and specifically 120 ℃, 150 ℃, 200 ℃, 250 ℃, 280 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃; in other embodiments of the present application, the thermal decomposition time may be 2-10h, may be 2-8h, may be 2-6h, may be 2-4h, and may specifically be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
In a second aspect of the present application, there is provided a method for preparing the graphite composite anode material, including:
heating a mixture of graphite, copper fluoride and metal nitride in an ammonia atmosphere to convert the copper fluoride into copper nitride;
and changing the ammonia gas atmosphere into a protective gas or reducing gas atmosphere, and continuously heating the mixture to decompose copper nitride and metal nitride to enable metal to be attached to the surface and/or the inside of graphite, so as to obtain the graphite composite anode material which can be directly used without cleaning.
In an ammonia atmosphere, copper nitride and ammonia react under the condition of heat treatment as follows:
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
ni in the metal nitride 3 N 2 At this stage, the decomposed metallic nickel can be directly released and attached to the surface and/or the inside of the graphite, and the reaction formula is as follows:
Ni 3 N 2 →Ni+N 2 (decomposition temperature 120 ℃ C. Or higher)
Cu obtained by the front stage heating treatment in a protective gas atmosphere 3 N and Fe 6 N 2 The metal copper and the metal iron are decomposed by continuous heating, and the reaction formula is as follows:
Cu 3 N→Cu+N 2 (decomposition temperature of 300 ℃ C. Or higher)
Fe 6 N 2 →Fe+N 2 (decomposition temperature of 400 ℃ C. Or higher)
Cu obtained by the front stage heating treatment in a reducing gas atmosphere 3 N and Zn 3 N 2 The metal copper and the metal zinc are decomposed by continuous heating, and the reaction formula is as follows:
Cu 3 N→Cu+N 2 (decomposition temperature of 300 ℃ C. Or higher)
Zn 3 N 2 +H 2 →Zn+NH 3 (decomposition temperature of 400 ℃ C. Or higher)
In certain embodiments of the present application, the temperature of the heating treatment in the ammonia atmosphere is 280-350 ℃, the time is selected to be 2-8h, and further selected to be 2-4h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h; the temperature may also be selected from 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃.
In certain embodiments of the present application, the heat treatment in the protective gas or reducing gas atmosphere is at a temperature of 400-650 ℃ for a time selected from 2-12 hours, and further selected from 2-10 hours or 2-8 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours; the temperature may also be selected from 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or 650 ℃.
In certain embodiments of the present application, the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide, methane, and sulfur monoxide; hydrogen may be selected for safety and environmental reasons.
In certain embodiments of the present application, the protective gas comprises one or more of nitrogen and a noble gas, such as nitrogen, argon, xenon, helium, neon, krypton, radon, and the like.
In certain embodiments of the present application, the method for preparing a graphite composite anode material comprises:
proportional CuF 2 ：Ni 3 N 2 /Zn 3 N 2 /Fe 6 N 2 10 (1-10) weighing raw materials, grinding the raw materials and graphite simultaneously, and uniformly doping the raw materials to obtain a mixture;
placing the ground mixture into an ammonia gas stream and heating for 2-8h at 120-350 ℃;
changing ammonia into nitrogen or hydrogen or rare gas, heating to 400-650 ℃ and heating for 2-12h;
the graphite composite anode material which can be directly used without cleaning is obtained.
In a third aspect of the present application, there is provided a negative electrode sheet, wherein the graphite composite negative electrode material described herein is used as an active material or the graphite composite negative electrode material prepared by the preparation method described herein is used as an active material.
In certain embodiments of the present application, the negative electrode tab includes a current collector and an active material coated on the current collector; wherein the current collector may be selected from a metal foil having good electrical conductivity, such as copper foil; the active material includes the graphite composite anode material, as well as a binder, a conductive agent, a solvent and a solvent, wherein the binder, the conductive agent, the solvent and the dosage thereof are selected according to the conventional method, the application is not particularly limited, for example, the binder is polyvinylidene fluoride (PVDF), styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC) and the like, the conductive agent is conductive carbon black (SP), acetylene black and the like, the solvent is N-methylpyrrolidone (NMP), deionized water and the like, and the graphite composite anode material comprises the conductive agent and the binder=8:1:1.
In a fourth aspect of the present application, there is provided a lithium battery comprising a positive electrode sheet, a separator, an electrolyte, and a negative electrode sheet as described herein; in certain embodiments of the present application, the lithium ion battery is a full battery, a pouch battery, or a coin battery.
In certain embodiments of the present application, the positive electrode sheet is a metallic lithium sheet or lithium iron phosphate, a high nickel ternary, lithium-rich manganese-based material, or the like; the diaphragm adopts a PP diaphragm or a cellegard series diaphragm; the electrolyte is LiPF with the concentration of 1.0-1.5mol/L 6 The solution is an electrolyte, such as LiPF in which Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as solvents in a volume ratio of 1:1 6 Is used as an electrolyte.
In each of the comparative experiments provided herein, unless specifically indicated otherwise, other experimental conditions, materials, etc. were consistent for comparison, except for the differences noted in each group. In addition, the materials used in the present application are all commercially available.
The following further describes a graphite composite anode material, a preparation method thereof, an anode piece and a lithium battery.
Example 1:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol), 2.04g of Ni 3 N 2 (0.01 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in an ammonia gas stream at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N，Ni 3 N 2 Decomposing into nickel metal by heating;
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
Ni 3 N 2 →Ni+N 2
changing ammonia in the quartz tube into nitrogen, heating to 450 ℃ and heating for 4 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
Cu 3 N→Cu+N 2
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Example 2:
100g of graphite is taken and 10.16g of CuF 2 (0.1 mol), 10.20g Ni 3 N 2 (0.05 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in ammonia gas flow at 300deg.C for 8 hr to give CuF 2 Conversion to Cu 3 N，Ni 3 N 2 Decomposing into nickel metal by heating;
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
Ni 3 N 2 →Ni+N 2
changing ammonia in the quartz tube into nitrogen, heating to 550 ℃ and heating for 8 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
Cu 3 N→Cu+N 2
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Example 3:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol), 20.40g Ni 3 N 2 (0.1 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in ammonia gas flow at 350deg.C for 2 hr to give CuF 2 Conversion to Cu 3 N，Ni 3 N 2 Decomposing into nickel metal by heating;
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
Ni 3 N 2 →Ni+N 2
changing ammonia in the quartz tube into nitrogen, heating to 650 ℃ and heating for 2 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
Cu 3 N→Cu+N 2
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Example 4:
100g of graphite and 15.2 g ofCuF of 4g 2 (0.15 mol), 11.23g of Zn 3 N 2 (0.05 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in an ammonia gas stream at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N；
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
Changing ammonia in the quartz tube into hydrogen, heating to 450 ℃ and heating for 4 hours to decompose copper nitride and zinc nitride into corresponding metals and attach the corresponding metals to graphite;
Cu 3 N→Cu+N 2
Zn 3 N 2 +H 2 →Zn+NH 3
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Example 5:
100g of graphite and 5.08g of CuF are taken 2 (0.05 mol), 10.89g of Fe 6 N 2 (0.03 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in an ammonia gas stream at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N；
CuF 2 +NH 3 →Cu 3 N+N 2 +NH 4 F
The ammonia in the quartz tube is changed into nitrogen, the temperature is raised to 450 ℃ and the heating is carried out for 4 hours, so that the copper nitride and the iron nitride are decomposed into corresponding metals and are attached to the graphite.
Cu 3 N→Cu+N 2
Fe 6 N 2 →Fe+N 2
The sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Comparative example 1:
placing 100g of graphite into a mortar, and grinding for 3 hours;
placing the ground graphite into an alumina vessel, placing the alumina vessel into a quartz tube, and heating the quartz tube in a nitrogen flow at 450 ℃ for 4 hours;
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Comparative example 2:
the difference from example 1 is only that graphite is doped with copper as one metal, specifically:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol) is put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in an ammonia gas stream at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N；
Changing ammonia in the quartz tube into nitrogen, heating to 450 ℃ and heating for 4 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Comparative example 3:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol), 1.02g of Ni 3 N 2 (0.005 moL) putting the mixture into a mortar, and grinding the mixture for 3 hours to uniformly dope the mixture;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in an ammonia gas stream at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N，Ni 3 N 2 Decomposing into nickel metal by heating;
changing ammonia in the quartz tube into nitrogen, heating to 450 ℃ and heating for 4 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Comparative example 4:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol), 22.40g Ni 3 N 2 (0.11 moL) is put into a mortar and ground for 3 hours to make the doping uniform;
will be groundPlacing the mixture into an alumina vessel, placing into a quartz tube, and heating in ammonia gas flow at 280 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N，Ni 3 N 2 Decomposing into nickel metal by heating;
changing ammonia in the quartz tube into nitrogen, heating to 450 ℃ and heating for 4 hours to decompose copper nitride into copper metal and attach the copper metal to graphite;
the sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Comparative example 5:
100g of graphite and 10.16g of CuF are taken 2 (0.1 mol) and 8.73g of GaN (0.1 mol) are put into a mortar and ground for 3 hours to make the doping uniform;
placing the ground mixture into an alumina vessel, placing into a quartz tube, and heating in ammonia gas flow at 1050 deg.C for 4 hr to give CuF 2 Conversion to Cu 3 N is further heated to decompose into copper metal and GaN is heated to decompose into gallium metal.
GaN→Ga+N 2 (decomposition temperature 1050 ℃ C. Or higher)
The sample in the quartz tube can be directly taken as a negative electrode material after being taken out, and cleaning is not needed.
Experimental example 1:
1. SEM test
By SEM testing the graphite anode material doped in example 3, it was observed that metal atoms were present on the surface of the graphite and between the layers, indicating that the nitride decomposed metal atoms and were uniformly distributed in the graphite, and SEM images of other example materials were substantially identical to example 3.
2. Physical and chemical property test
The graphite composite anode materials of examples 1 to 5 and the graphite anode materials of comparative examples were tested for conductivity, tap density, specific surface area, and particle size according to the test method in the standard GB/T-24533-2019 "lithium ion battery graphite-based anode materials". The test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the conductivity of the metal doped graphite composite anode materials prepared in examples 1-5 is significantly higher than that of the comparative examples, wherein the conductivity of the materials in examples 1-3 is 1-2 orders of magnitude higher than that of the materials in each comparative example, and the reasons are probably that the conductivity of the metals doped in the materials in examples is higher and the synergistic effect between the metals, and the combined effect of the two reduces the impedance of graphite and improves the conductivity of the graphite; the density of the metal element is high, and the tap density can be improved by depositing the metal element on the graphite. In addition, since the particles of the metal nitride are smaller than the graphite, the trace amount of nitride which is not decomposed can fill the gaps between the graphite and the graphite, thereby improving the tap density.
3. First charge and discharge performance test for button cell
Graphite anode materials in examples 1 to 5 and comparative examples 1 to 5 were assembled into button cells respectively designated as A1, A2, A3, A4, A5 and B1, B2, B3, B4, B5;
the assembly method comprises the following steps: adding a binder, a conductive agent and a solvent into a graphite anode material, stirring and pulping, coating the graphite anode material on a copper foil, and drying and rolling the graphite anode material to obtain the anode sheet. The binder used was polyvinylidene fluoride (PVDF), the conductive agent was acetylene black, the solvent was N-methylpyrrolidone (NMP), and the negative electrode materials used were graphite negative electrode materials in examples and comparative examples, respectively. The proportion of each component is as follows: a negative electrode material; conductive agent: binder=8:1:1, electrolyte is LiPF 1mol/L 6 The metal lithium sheet is the positive electrode of the button cell, and the separator adopts the cellgard 2400. Assembly of the coin cell assembled into a coin cell in a glove box with both argon and water contents below 0.1 ppm. The electrochemical performance test is carried out on a Wuhan blue electric CT2001A type battery tester, the charge-discharge voltage range is 0.05V to 2V, and the charge-discharge multiplying power is 1C.
TABLE 2
| A1 | A2 | A3 | A4 | A5 | |
| Specific capacity for initial discharge (mAh/g) | 383.7 | 397.9 | 416.1 | 375.4 | 367.4 |
| First time efficiency (%) | 99.1 | 99.3 | 99.4 | 99.5 | 98.9 |
| B1 | B2 | B3 | B4 | B5 | |
| Specific capacity for initial discharge (mAh/g) | 354.2 | 362.9 | 356.2 | 417.5 | 357.5 |
| First time efficiency (%) | 98.4 | 98.5 | 98.3 | 97.2 | 98.5 |
As can be seen from table 2, compared with comparative example 1, the lithium ion batteries using the double doped graphite composite materials prepared in examples 1 to 5 as graphite negative electrode materials have significantly higher initial discharge specific capacity and initial charge-discharge efficiency than the graphite composite material prepared in comparative example 1. The reason for this is that the metal doped between the graphite layers can promote the conductivity of the lithium ion battery, thereby improving the first efficiency thereof; the specific capacity of the non-decomposed nitride is higher than that of graphite, so that the tap density of the non-decomposed nitride can be improved, and the specific capacity of the graphite anode material is improved.
Compared with comparative example 2, the lithium ion battery taking the double-doped graphite composite material prepared in examples 1-5 as the graphite anode material has the first discharge specific capacity and the first charge-discharge efficiency which are obviously higher than those of the graphite composite material prepared in comparative example 2, and shows that the performance improvement effect of double doping on the graphite anode material is better than that of single doping.
From examples 1-3, it can be seen that compared to comparative example 3, the trace amount of non-copper metal, while increasing the capacity of the graphite material, is less elevated;
as can be seen from examples 1 to 3, when the amount of the non-copper metal used is too large, the first-time discharge specific capacity can be improved, but the first-time efficiency is lowered, and a negative electrode material having good first-time discharge specific capacity and first-time efficiency cannot be obtained.
It can be seen from examples 1-5 compared to comparative example 5 that the metal nitrides used in the present application can reduce the nitrides to metals at lower decomposition temperatures, greatly save energy, and can better enhance the electrochemical properties of graphite than the non-limiting other nitrides.
4. Soft package battery cycle performance and multiplying power performance test
Negative electrode sheets were prepared using the graphite materials of examples 1 to 5 and comparative examples as negative electrode materials. With ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) As positive electrode, with LiPF 6 Solution (EC+DEC solvent, volume ratio 1:1, liPF) 6 Concentration 1.3 mol/L) is an electrolyte, and cellgard 2400 is a separator, and assembled into pouch cells A1, A2, A3, A4, A5 and B1, B2, B3, B4, B5.
Cycle performance test conditions: the discharge current is 2C/2C, the voltage range is 2.6-4.2V, and the cycle number is 500 weeks.
Rate performance test conditions: charging rate: 1C/2C/3C/5C/8C, discharge multiplying power 1C; voltage range: 2.6-4.2V.
TABLE 3 Table 3
As can be seen from table 3, the cycling performance of the soft-package battery prepared from the graphite composite anode material is obviously superior to that of the comparative example, and in the aspect of the cycling performance, two metals are deposited on the surface of graphite and between the layers, so that the electronic conductivity can be improved, and the side reaction of the soft-package battery is reduced; meanwhile, the metal nitride promotes the intercalation and deintercalation of lithium ions in the charge and discharge process, reduces impedance and improves the structural stability of the material, thereby improving the cycle performance.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A graphite composite negative electrode material is characterized in that the surface and/or the interior of graphite is doped with metal generated by thermal decomposition of copper fluoride and metal nitride and non-decomposed metal nitride; the metal nitride is selected from Ni 3 N 2 、Zn 3 N 2 、Fe 6 N 2 One or two or more of them.
2. The graphite composite anode material according to claim 1, wherein the molar ratio of copper fluoride to metal nitride is 10 (1-10).
3. The graphite composite negative electrode material according to claim 1, wherein the ratio of graphite to copper fluoride is 100g (0.05 to 0.15 mol).
4. The graphite composite anode material according to claim 1, wherein the thermal decomposition environment is 400-650 ℃.
5. The method for preparing a graphite composite anode material as claimed in claim 1, comprising:
heating a mixture of graphite, copper fluoride and metal nitride in an ammonia atmosphere to convert the copper fluoride into copper nitride;
and changing the ammonia gas atmosphere into a protective gas or reducing gas atmosphere, and continuously heating the mixture to decompose copper nitride and metal nitride to enable metal to be attached to the surface and/or the inside of graphite, so as to obtain the graphite composite anode material which can be directly used without cleaning.
6. The method according to claim 5, wherein the heating treatment temperature in the ammonia atmosphere is 280 to 350 ℃.
7. The method according to claim 5, wherein the heat treatment temperature in the protective gas or the reducing gas atmosphere is 100 to 650 ℃.
8. The method according to claim 5, wherein the reducing gas comprises one or more of hydrogen, carbon monoxide, hydrogen sulfide, methane, and sulfur monoxide.
9. A negative electrode sheet characterized in that a graphite composite negative electrode material according to any one of claims 1 to 4 or a graphite composite negative electrode material prepared by the preparation method according to any one of claims 5 to 8 is used as an active material.
10. A lithium battery comprising a positive electrode sheet, a separator, an electrolyte, and the negative electrode sheet of claim 9.
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