CN115172683A - Lithium ion battery negative electrode material, lithium ion battery and preparation method - Google Patents

Lithium ion battery negative electrode material, lithium ion battery and preparation method Download PDF

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CN115172683A
CN115172683A CN202210728451.1A CN202210728451A CN115172683A CN 115172683 A CN115172683 A CN 115172683A CN 202210728451 A CN202210728451 A CN 202210728451A CN 115172683 A CN115172683 A CN 115172683A
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ion battery
lithium ion
negative electrode
electrode material
zinc
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赵若
宋满荣
高磊
卞均操
朱金龙
赵予生
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Southwest University of Science and Technology
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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
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
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    • 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

A lithium ion battery cathode material, a lithium ion battery and a preparation method belong to the technical field of secondary batteries. The lithium ion battery negative electrode material comprises an MOF material obtained by reacting zinc salt and 1H-1,2,3 triazole, and a porous carbon material doped with zinc and zinc cyanide is obtained after carbonization. The porous carbon material has good electronic conductivity and larger volume expansion tolerance, and zinc cyanide have the lithium affinity characteristic, so that the nucleation potential of lithium metal can be reduced, the uniform deposition and stripping of lithium ions are realized, the formation and growth of lithium dendrites are avoided, and the cycle performance and the safety performance of the lithium ion battery are improved.

Description

Lithium ion battery negative electrode material, lithium ion battery and preparation method
Technical Field
The application relates to the technical field of secondary batteries, in particular to a lithium ion battery cathode material, a lithium ion battery and a preparation method.
Background
The secondary battery, especially the lithium ion battery, has the advantages of high energy density, high output voltage, no memory effect, no environmental pollution and the like, can be used for portable electronic equipment, can also be used as an energy storage component of an electric automobile power supply and equipment such as solar energy or wind energy and the like, and has good application prospect.
The traditional lithium ion battery generally takes graphite as a negative electrode material and layered lithium cobaltate (LiCoO) 2 ) Or lithium iron phosphate (LiFePO) 4 ) The lithium ion battery is used as a positive electrode material and takes a nonaqueous lithium ion conductive medium as an electrolyte.
The graphite material has a good layered structure and electrical conductivity, and the theoretical specific capacity of the graphite material is 372mAh/g. However, the conventional graphite electrode is easy to generate the co-intercalation phenomenon of lithium ions and solvent molecules, and the growth of lithium dendrites pierces through a diaphragm to easily cause short circuit of the battery, so that the practical application of the lithium ion battery is restricted. In addition, with repeated intercalation and deintercalation of lithium ions, the graphite structure is continuously and repeatedly expanded and contracted, so that graphite sheets are easy to fall off to generate rapid capacity attenuation of electrode materials.
Disclosure of Invention
Based on the defects, the application provides the lithium ion battery cathode material, the lithium ion battery and the preparation method, so as to partially or completely solve the problem that the performance of the lithium ion battery is influenced by the cathode material in the related technology.
The application is realized as follows:
in a first aspect, examples of the present application provide a lithium ion battery anode material comprising a porous carbon material doped with zinc and zinc cyanide.
In the implementation process, the porous carbon material has good electronic conductivity, and the use of the porous carbon material as the negative electrode of the lithium ion battery can increase the conductivity between the current collector and the negative electrode. And the porous carbon material has larger tolerance to the volume expansion of the lithium ion battery, reduces the expansion probability of the lithium ion battery, and improves the long-term circulation stability and safety of the battery.
The zinc and the zinc cyanide are doped in the porous carbon material, and have the lithium affinity characteristic, so that the nucleation potential of lithium metal can be reduced, the uniform deposition and stripping of lithium ions are realized, the formation and the growth of lithium dendrites are avoided, and the cycle performance and the safety performance of the lithium ion battery are improved. And the zinc and zinc cyanide doped porous material can prevent the solvent from being co-embedded, so that the coulombic efficiency of the battery is further improved.
The lithium ion battery cathode material can enable the lithium ion battery to have longer cycle stability and safety.
With reference to the first aspect, in a first possible embodiment of the first aspect of the present application, the porous carbon material is in a hierarchical pore structure.
In a second possible embodiment of the first aspect of the present application in combination with the first aspect, the hierarchical pore structure comprises first pores having a pore size of 0.5 to 50 μm, and second pores having a pore size of 2 to 500 nm.
In the implementation process, the porous carbon material is of a hierarchical pore structure, the hierarchical pore structure comprises first pores with the pore diameter of 0.5-50 microns and second pores with the pore diameter of 2-500 nm, the specific surface area of the porous carbon material can be improved while the structural stability of the porous carbon material is ensured and the structure is prevented from collapsing, more active sites are provided for the insertion and the extraction of lithium ions, and the stability of the lithium ion battery is further improved.
In a second aspect, examples of the present application provide a method of preparing a lithium ion battery anode material, comprising:
the method comprises the following steps: dissolving zinc salt and 1H-1,2,3 triazole in a solvent, and fully reacting to obtain an MOF material;
step two: heating and activating the MOF material, and then calcining the MOF material in an inert gas atmosphere to obtain the porous carbon material doped with zinc and zinc cyanide.
In the implementation process, a porous complex which has a carbon source and a metal source (metal ions) and has a periodic network structure can be obtained through the reaction of zinc salt and 1H-1,2,3 triazole, so that a zinc and zinc cyanide doped porous carbon material can be obtained through a carbonization process in an inert atmosphere at the later stage. The porous carbon material has a good pore structure and conductivity, and when the porous carbon material is used as a lithium ion battery cathode, the conductivity between a current collector and the cathode can be increased, the probability of battery failure caused by expansion of the lithium ion battery is reduced, and the long-cycle stability and the safety of the battery are improved. The zinc and the zinc cyanide have the lithium-philic characteristic, the nucleation potential of lithium metal can be reduced, the uniform deposition and stripping of lithium ions at the porous carbon are realized, the formation and growth of lithium dendrites are avoided, and the cycle performance and the safety performance of the lithium ion battery are improved.
In a first possible embodiment of the second aspect of the present application in combination with the second aspect, in step one, 1H-1,2,3 triazole and Zn in zinc salt 2+ In a molar ratio of 1: (2-5).
In the implementation process, the molar ratio of 1: (2-5) 1H-1,2,3 triazole and Zn 2+ The MOF material is formed by mixing the materials in a solvent, so that impurities formed after the MOF material is carbonized due to excessive 1H-1,2,3 triazole are avoided, or zinc cyanide cannot be formed after the MOF material is carbonized due to too little 1H-1,2,3 triazole, and the beneficial effects of the obtained porous carbon material on the performance and safety of a lithium ion battery are reduced.
In a second possible embodiment of the second aspect of the present application in combination with the second aspect, the solvent comprises ethanol, water, ammonia, and N, N-dimethylformamide;
alternatively, the ratio of ethanol: water: ammonia water: the volume ratio of N, N-dimethylformamide is 10; the mass ratio of the zinc salt to the water is 1.
In the realization process, the zinc salt and the 1H-1,2,3 triazole are dissolved in ethanol, water and ammoniaIn the solvent of water and N, N-dimethylformamide, the zinc salt and the 1H-1,2,3 triazole can be uniformly dispersed, so that the zinc salt and the 1H-1,2,3 triazole can be conveniently and fully reacted to form the MOF material. And the solvent is added with ammonia water which can neutralize hydrogen and NH in the 1H-1,2,3 triazole 4 + The ions combine with the anions in the zinc salt to accelerate the reaction process.
Limiting ethanol in solvent: water: ammonia water: the volume ratio of N, N-dimethylformamide is 10.
In a third possible embodiment of the second aspect of the present application in combination with the second aspect, the temperature of the calcination in step two is in the range of 500 to 700 ℃.
In a fourth possible embodiment of the second aspect of the present application in combination with the second aspect, the inert atmosphere is argon.
In the implementation process, the MOF material is calcined at the temperature of 500-700 ℃, so that the MOF material can be carbonized to obtain porous carbon, zinc and zinc cyanide, and the phenomenon that the zinc or zinc cyanide reacts with other chemical substances to form impurities due to incomplete carbonization at too low temperature or too high temperature can be avoided.
Set up inert atmosphere into argon gas, compare in inert gas such as nitrogen gas, argon gas has better chemical stability, can reduce the formation probability of carbonization in-process impurity.
In a third aspect, implementations of the present application provide a lithium ion battery comprising:
the negative electrode is made of the negative electrode material of the lithium ion battery provided by the first aspect or the second aspect;
and the negative electrode is arranged on one surface of the current collector piece.
In the implementation process, the negative electrode made of the lithium ion battery negative electrode material provided by the first aspect or the second aspect is arranged on one surface of the current collector sheet, and the porous carbon material has good electronic conductivity, so that the current collector and the negative electrode have good conductivity, and the charge and discharge performance of the lithium ion battery is improved. And the porous carbon material has larger tolerance to the volume expansion of the lithium ion battery, and reduces the expansion probability of the lithium ion battery, so that the lithium ion battery has good long-cycle stability and safety. The zinc and zinc cyanide doped porous material can reduce the nucleation potential of lithium metal, realize the uniform deposition and stripping of lithium ions, avoid the formation and growth of lithium dendrites and improve the cycle performance and safety performance of the lithium ion battery because the zinc and the zinc cyanide have the lithium-philic characteristic. The zinc and zinc cyanide doped porous carbon material can also prevent the co-intercalation of a solvent and lithium ions, so that the lithium ion battery has higher coulombic efficiency.
In a fourth aspect, implementations of the present application provide a method of making a lithium ion battery, comprising:
mixing the lithium ion battery negative electrode material obtained by the preparation method of the lithium ion battery negative electrode material provided by the first aspect or the second aspect and a binder in water to obtain a first mixture;
optionally, the weight ratio of the lithium ion battery negative electrode material to the binder is 8:1;
the first mixture is applied to one of the surfaces of the current collector sheet and vacuum dried.
In the implementation process, the zinc and zinc cyanide doped porous carbon material provided by the first aspect or the second aspect and the binder are mixed in water, so as to form a coating liquid in which the porous carbon material and the binder are uniformly mixed, and a firm and uniformly distributed negative electrode material is coated on the surface of the current collector sheet. In the dissolving process, water is used as a solvent, so that the use of organic solvents such as PVDF and the like can be avoided, the concept of green new energy development is met, and the harm and pollution of organic matters are reduced.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the prior art of the present application, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a flow chart of the preparation of an electrode sheet of a lithium ion battery according to the present application;
FIG. 2 is an XRD diffraction pattern of the lithium ion battery negative electrode material obtained in example 1;
fig. 3 is an SEM image of the negative electrode material of the lithium ion battery obtained in example 1;
FIG. 4 is a pore size distribution diagram of the negative electrode material for a lithium ion battery obtained in example 1;
fig. 5 is a plot of coulombic efficiency versus cycle count for the lithium ion battery provided in example 4.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following specifically describes the lithium ion battery negative electrode material, the lithium ion battery and the preparation method provided by the example of the present application:
the lithium ion battery has the advantages of high energy density, high output voltage, no memory effect, no environmental pollution and the like, and has good application prospect. The traditional lithium ion battery generally takes graphite as a negative electrode material and layered lithium cobaltate (LiCoO) 2 ) Or lithium iron phosphate (LiFePO) 4 ) The lithium ion battery is used as a positive electrode material and takes a nonaqueous lithium ion conductive medium as an electrolyte. During charging, lithium ions are extracted from the positive electrode and then are inserted into the negative electrode, and during discharging, the lithium ions are released from the negative electrode and inserted into the positive electrode, so that an insertion and extraction reciprocating process is formed between electrode materials.
The graphite material has a good layered structure and electrical conductivity, and the theoretical specific capacity of the graphite material is 372mAh/g. However, the inventors found that although the graphite material has a high theoretical specific capacity, the graphite electrode is prone to generate a co-intercalation phenomenon of lithium ions and solvent molecules, and uneven carbon deposition easily causes growth of lithium dendrites to pierce through the separator, which easily causes short circuit of the battery and consumes the electrode, thereby limiting practical application of the lithium ion battery. In addition, with repeated intercalation and deintercalation of lithium ions, the graphite structure is continuously and repeatedly expanded and contracted, so that graphite sheets are easy to fall off to generate rapid capacity attenuation of electrode materials.
Based on the above, the inventor provides a lithium ion battery negative electrode material, and provides a porous carbon material doped with zinc and zinc cyanide. The porous carbon material has good electronic conductivity and larger tolerance to volume expansion of the lithium ion battery, and the zinc cyanide have the lithium affinity characteristic, so that the nucleation potential of lithium metal can be reduced, the uniform deposition and stripping of lithium ions can be realized, the formation and growth of lithium dendrites can be avoided, and the cycle performance and the safety performance of the lithium ion battery can be improved.
The following describes the preparation method of the negative electrode material of the lithium ion battery in further detail with reference to fig. 1.
S1, dissolving zinc salt and 1H-1,2,3 triazole in a solvent, and fully reacting to obtain the MOF material.
The porous complex with a carbon source and a metal source (metal ions) and a periodic network structure can be obtained through the full reaction of zinc salt and 1H-1,2,3 triazole.
The application does not limit the specific type of the zinc source, and related personnel can ensure Zn 2+ Can be correspondingly selected according to the requirement under the condition of fully reacting with 1H-1,2,3 triazole to form MOF material.
In one possible embodiment, the zinc salt is selected from ZnF 2 、ZnCl 2 、ZnBr 2 、ZnI 2 、 Zn(NO 3 ) 2 、Zn(NO 3 ) 2 ·6H 2 O and Zn (OAc) 2 ·6H 2 One or more of O. Illustratively, znCl is added 2 Mixing with 1H-1,2,3 triazole in solvent.
The addition ratio of the zinc salt and the 1H-1,2,3 triazole is not limited in the application, and relevant personnel can select the zinc salt and the 1H-1,2,3 triazole correspondingly according to needs.
In one possible embodiment, 1H-1,2,3 triazole and Zn in zinc salt 2+ In a molar ratio of 1: (2E ^ E5)。
Mixing a mixture of 1: (2-5) 1H-1,2,3 triazole and Zn 2+ The MOF material is formed by mixing in a solvent, so that impurities are prevented from being formed after the MOF material is carbonized due to excessive 1H-1,2,3 triazole, or zinc cyanide cannot be formed after the MOF material is carbonized due to too little 1H-1,2,3 triazole, and the beneficial influence of the obtained porous carbon material on the performance and safety of a lithium ion battery is reduced.
Exemplary 1H-1,2,3 triazole with Zn in zinc salt 2+ Including but not limited to a molar ratio of 1:2. 1:2.5, 1: 3. 1:4 and 1:5, or a range between any two.
The application does not limit the specific type of the solvent, and related personnel can correspondingly select the zinc salt and the 1H-1,2,3 triazole according to requirements under the condition of ensuring that the zinc salt and the 1H-1,2,3 triazole can be uniformly dispersed and reacted to obtain the MOF material.
In one possible embodiment, the solvent includes ethanol, water, ammonia, and N, N-dimethylformamide.
The zinc salt and the 1H-1,2,3 triazole are dissolved in the solvent of ethanol, water, ammonia water and N, N-dimethylformamide, so that the zinc salt and the 1H-1,2,3 triazole can be uniformly dispersed, and the zinc salt and the 1H-1,2,3 triazole can be conveniently and fully reacted to form the MOF material. And the solvent is added with ammonia water which can neutralize H and NH in 1H-1,2,3 triazole 4 + The ions combine with the anions in the zinc salt to accelerate the reaction process.
The present application does not limit the addition ratio of ethanol, water, ammonia and N, N-dimethylformamide in the solvent, and in one possible embodiment, the ratio of ethanol: water: ammonia water: the volume ratio of the N, N-dimethylformamide is 10.
The zinc salt with a proper proportion is added into the solvent, so that the reaction process can be accelerated by uniform dispersion, the generation of side reactants can be reduced, and the beneficial effects of the porous carbon material doped with zinc and zinc cyanide on the performance and safety of the lithium ion battery can be increased.
Alternatively, in one possible embodiment, the solvent includes any one or more of ethanol, water, and N, N-dimethylformamide. For example, the solvent includes ethanol and water, or the solvent includes ethanol and N, N-dimethylformamide.
The application does not limit the specific reaction conditions of the zinc salt and the 1H-1,2,3 triazole, and in one possible implementation mode, in order to accelerate the reaction speed and promote the full reaction of reactants, the mixed solution of the zinc salt and the 1H-1,2,3 triazole in the solvent can be placed at room temperature for standing, and then the centrifugal stirring is carried out for 5-10 min at the rotating speed of 8000rpm, so as to obtain the centrifugal precipitate. Or standing the mixed solution at room temperature for more than 20h, and filtering the solution after reaction to obtain a precipitate.
In one possible embodiment, the precipitate obtained after the standing reaction may be washed to remove impurities such as a solvent attached to the reactant. The cleaning agent for cleaning the precipitate may be ethanol.
S2, heating and activating the MOF material, and then calcining in an inert gas atmosphere to obtain the porous carbon material doped with zinc and zinc cyanide.
And (3) heating and activating the MOF material obtained in the step (S1), removing volatile solvents or impurities to a certain extent, obtaining a dry MOF material, promoting the activity of the MOF material, and then carbonizing to obtain the high-performance lithium ion battery cathode material with zinc and zinc cyanide implanted in the porous carbon material.
The application does not limit the specific conditions of the heating activation, and in one possible embodiment, the solid precipitate obtained in S1 (MOF material) is placed in a drying oven for drying. In order to avoid side reactions during the drying process, the drying may be carried out in a vacuum drying oven. The drying temperature is not suitable to be too high, and the drying can be carried out for 6 to 15 hours at 80 ℃. Alternatively, the drying may be performed directly in a tube furnace, so that the carbonization treatment may be further performed by the tube furnace after the drying is completed.
The application is not limited to specific calcination conditions, and the relevant personnel can make corresponding adjustments while ensuring that the MOF material can be carbonized to obtain zinc and zinc cyanide doped porous carbon material.
In one possible embodiment, the MOF material obtained in S1 can be placed in a furnace tube of a tube furnace, which is then closed and the tube furnace is ventilated to ensure that the atmospheric conditions within the tube furnace are inert. And heating the MOF material in the furnace tube to a carbonization temperature at a certain heating rate, and carbonizing.
In one possible embodiment, the MOF material is heated to a temperature of 500-700 ℃ at a ramp rate of 5-10 ℃/min and held for 1-3 hours.
Illustratively, the calcination temperature includes, but is not limited to, a range between one or any two of 500 ℃, 600 ℃, 650 ℃, and 700 ℃.
The application is not limited to a particular type of inert atmosphere during the carbonization process, and in one possible embodiment, the inert atmosphere includes, but is not limited to, one or more of helium, neon, argon, krypton, xenon, and radon. Preferably, the MOF material is subjected to carbonization calcination under an argon atmosphere.
Examples of the present application provide a lithium ion battery including a current collector sheet and a negative electrode disposed on one of surfaces of the current collector sheet. The negative electrode is made of a lithium ion battery negative electrode material of a porous carbon material doped with zinc and zinc cyanide.
The current collector sheet is not limited to a specific material, and in one possible embodiment, the current collector sheet may be selected from a metal conductor material such as copper, aluminum, nickel, and stainless steel, or a semiconductor material such as carbon, and a composite material. For example, a negative electrode may be provided on one of the surfaces of the copper current collector sheet.
The present application does not limit the type of distance of the lithium ion battery, which in one possible embodiment further comprises a positive current collector, a positive electrode and a solid/liquid electrolyte. The type of the positive electrode collector may be the same as the above-described collector sheet. The positive electrode can be selected from lithium nickelate, lithium cobaltate, lithium titanate, lithium iron phosphorus, and the like.
The following provides a further detailed description of the method for manufacturing the lithium ion battery provided in this example with reference to fig. 1.
And S3, mixing the lithium ion battery negative electrode material and the binder in water to obtain a first mixture.
The lithium ion battery negative electrode material and the binder are mixed in water so as to be uniformly coated on the current collector sheet, and a stable negative electrode is formed on the current collector sheet. And conductive carbon black is not used, so that the production cost and the resource saving of the lithium ion battery are reduced, and a good vision is provided for the industrialization of the lithium ion battery.
In addition, water is used as a solvent, the method conforms to the concept of green new energy development, and simultaneously reduces the harm and pollution of organic matters in the production process of the lithium ion battery.
The application does not limit the specific choice of binder, which in one possible embodiment may be sodium polyacrylate.
The content ratio of the lithium ion battery negative electrode material to the binder is not limited, and in one possible embodiment, the weight ratio of 1:8, mixing the sodium polyacrylate with the lithium ion battery negative electrode material in water.
The content of water is not limited, and related personnel correspondingly select the coating liquid conveniently and the lithium ion battery cathode material and the binder are dispersed.
And S4, coating the first mixture on one surface of the current collector sheet, and drying in vacuum.
And coating the first mixture on one surface of the current collector sheet, and then performing vacuum drying to enable the negative electrode material to be uniformly attached to the surface of the current collector sheet, so as to obtain the electrode sheet.
The application is not limited to how the first mixture is applied to one of the surfaces of the current collector sheet, and in one possible embodiment, the application method may include spin coating, gravure coating, dip coating, and the like.
In one possible embodiment, the first mixture is coated on a copper current collector sheet with a coating blade having a thickness of 1000 μm using a commercial coating machine, vacuum-dried at a temperature of 80 ℃ for 12 hours, rolled and then sliced to obtain an electrode sheet.
The lithium ion battery negative electrode material and the lithium ion battery of the present application are further described in detail with reference to the following examples.
Example 1
The embodiment 1 of the application provides a lithium ion battery anode material, which is prepared by the following preparation method:
(1) Ethanol, water, ammonia water, N-dimethylformamide were mixed in a volume ratio of 10.
(2) Reacting ZnCl 2 And (2) adding the mixed solution obtained in the step (1), and stirring and mixing to obtain a second mixed solution. Wherein ZnCl is 2 The mass ratio of the water to the water in the step (1) is 1:15.
(3) Dropwise adding 1H-1,2,3 triazole into the mixed solution obtained in the step (2), and stirring and mixing. Wherein, 1H-1,2,3 triazole and ZnCl added in the step (2) 2 Middle Zn 2+ In a molar ratio of 1:2.
(4) And (4) placing the mixed solution obtained in the step (3) at room temperature, and stirring for 20 hours. Then, the mixture was centrifuged at 8000rpm for 5min to obtain a precipitate. Washing the precipitate with ethanol to obtain the MOF material.
(5) And (3) placing the MOF material obtained in the step (4) in a drying oven, and drying at the temperature of 80 ℃ for 10h. And then placing the dried and activated MOF material in a furnace tube of a tube furnace, adjusting the atmosphere state in the furnace tube to be argon, heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, and naturally cooling.
Fig. 2 is an XRD diffraction pattern of the lithium ion battery negative electrode material obtained in example 1, fig. 3 is an SEM image of the lithium ion battery negative electrode material obtained in example 1, and fig. 4 is a pore size distribution diagram. It can be seen from fig. 2 that the lithium ion battery negative electrode material provided in this example contains zinc and zinc cyanide, and it can be seen from fig. 3 that the lithium ion battery negative electrode material provided in example 1 of this application has a hierarchical pore structure, which includes first pores with a pore diameter of 0.5 to 50um, and second pores with a pore diameter of 2 to 500nm (the first pores and the second pores do not refer to the number of pores, but refer to the pore diameter type of the pores). As can be seen from FIG. 4, the second pores (2 to 500 nm) are dominant in the porous carbon material.
Example 2
Example 2 of the present application provides a negative electrode material for a lithium ion battery, which is different from example 1 in thatIn the step (3), 1H-1,2,3 triazole and ZnCl added in the step (2) 2 Middle Zn 2+ In a molar ratio of 1:5.
example 3
The embodiment 3 of the present application provides a lithium ion battery negative electrode material, which is different from the embodiment 2 in that in the step (5), the temperature is raised to 700 ℃ at a temperature rise rate of 5 ℃/min, the temperature is maintained for 3 hours, and the material is naturally cooled.
Example 4
Embodiment 4 of the present application provides a lithium ion battery (half cell structure) prepared by the following method:
a, mixing the components in a mass ratio of 1:8 sodium polyacrylate was mixed with the negative electrode material for lithium ion battery obtained in example 1 in water to prepare a coating liquid.
b, coating the coating liquid obtained in the step a on a copper current collector sheet by using a coating machine, drying for 12 hours at the temperature of 80 ℃ in a vacuum environment, and then preparing an electrode sheet with the diameter of 12 mm.
c in glove box (O) 2 <0.01ppm,H 2 O<0.01 ppm), assembling the electrode sheet provided in the step b and a lithium metal sheet with the diameter of 12mm (a half-cell structure), and obtaining the lithium ion battery.
Experimental example 1
The lithium ion battery provided in example 4 was operated at a voltage of-0.01 to 1V and a current density of 1mA cm -2 The cycle performance test was performed under the conditions (1), and the test results are shown in fig. 5.
As can be seen from fig. 5, the coulombic efficiency of the lithium ion battery provided in example 4 after 450 cycles is greater than 99%, which is superior to the cycle performance of the porous carbon negative electrode material in the prior art (in the lithium ion battery constructed by the porous carbon negative electrode material obtained by carbonizing the Zn-MOF material in the prior art, the coulombic efficiency after 100 cycles of stable cycle is lower than 90%). And compared with the negative electrode made of the existing graphite material, the negative electrode made of the existing graphite material can only stably circulate for about 80 circles (see the technical document of Single-Atom Reversible lithium ions heated stabilized lithium antibodies, advanced Energy Materials, 2022.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. The lithium ion battery negative electrode material is characterized by comprising a porous carbon material, wherein the porous carbon material is doped with zinc and zinc cyanide.
2. The lithium ion battery anode material according to claim 1, wherein the porous carbon material has a hierarchical pore structure.
3. The negative electrode material of a lithium ion battery as claimed in claim 2, wherein the hierarchical pore structure comprises first pores with a pore diameter of 0.5-50 μm and second pores with a pore diameter of 2-500 nm.
4. A preparation method of a lithium ion battery negative electrode material is characterized by comprising the following steps:
the method comprises the following steps: dissolving zinc salt and 1H-1,2,3 triazole in a solvent, and fully reacting to obtain an MOF material;
step two: and heating and activating the MOF material, and then calcining the MOF material in an inert gas atmosphere to obtain the porous carbon material doped with zinc and zinc cyanide.
5. The preparation method of the anode material for the lithium ion battery of claim 4, wherein in the first step, the 1H-1,2,3 triazole and Zn in the zinc salt 2+ In a molar ratio of 1: (2-5).
6. The method for preparing the negative electrode material for the lithium ion battery according to claim 5, wherein the solvent comprises ethanol, water, ammonia water, and N, N-dimethylformamide;
alternatively, the ethanol: the water: the ammonia water: the volume ratio of the N, N-dimethylformamide is 10; the mass ratio of the zinc salt to the water is 1.
7. The method for preparing the negative electrode material of the lithium ion battery according to claim 6, wherein the temperature of the calcination in the second step is 500-700 ℃.
8. The method for preparing the negative electrode material of the lithium ion battery according to claim 7, wherein the inert atmosphere is argon.
9. A lithium ion battery, comprising:
a negative electrode made of the lithium ion battery negative electrode material provided by any one of claims 1 to 3; or, the negative electrode is made of the lithium ion battery negative electrode material obtained by the preparation method of the lithium ion battery negative electrode material provided by any one of claims 4 to 8;
and the negative electrode is arranged on one surface of the current collector piece.
10. A method for preparing a lithium ion battery is characterized by comprising the following steps:
mixing the lithium ion battery negative electrode material provided in any one of claims 1 to 3 and a binder in water to obtain a first mixture;
or, mixing the lithium ion battery negative electrode material obtained by the method for preparing a lithium ion battery negative electrode material provided in any one of claims 4 to 8 and a binder in water to obtain a first mixture;
optionally, the weight ratio of the lithium ion battery negative electrode material to the binder is 8:1;
the first mixture is applied to one of the surfaces of the current collector sheet and vacuum dried.
CN202210728451.1A 2022-06-24 2022-06-24 Lithium ion battery negative electrode material, lithium ion battery and preparation method Pending CN115172683A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115928463A (en) * 2022-11-30 2023-04-07 江苏润禾纺织实业有限公司 Low-salt low-alkali energy-saving environment-friendly dyeing process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115928463A (en) * 2022-11-30 2023-04-07 江苏润禾纺织实业有限公司 Low-salt low-alkali energy-saving environment-friendly dyeing process
CN115928463B (en) * 2022-11-30 2023-09-26 江苏润禾纺织实业有限公司 Low-salt low-alkali energy-saving environment-friendly dyeing process

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