CN110061199B - Metal-carbon composite anode material and preparation method and application thereof - Google Patents

Metal-carbon composite anode material and preparation method and application thereof Download PDF

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CN110061199B
CN110061199B CN201810057247.5A CN201810057247A CN110061199B CN 110061199 B CN110061199 B CN 110061199B CN 201810057247 A CN201810057247 A CN 201810057247A CN 110061199 B CN110061199 B CN 110061199B
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bituminous coal
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CN110061199A (en
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刘晓剑
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Hunan Jinye High Tech Co ltd
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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 invention belongs to the field of battery materials, and particularly relates to a preparation method of a metal-carbon composite anode material, which comprises the steps of mixing bituminous coal with a metal source to obtain a mixture; the mixture is sequentially subjected to primary sintering, secondary sintering and tertiary sintering; obtaining the composite anode material; wherein the temperature of the first-stage sintering is 300 ℃ or lower; the temperature of the second-stage sintering is 400-600 ℃; the temperature of the three-stage sintering is 700-1200 ℃. The invention also comprises a negative electrode material prepared by the preparation method and application of the negative electrode material in preparation of a negative electrode of a lithium ion battery. The invention adopts bituminous coal as raw material; the raw material is matched with a metal source, and under the special three-stage sintering mechanism, the battery anode material with excellent electrical properties can be prepared.

Description

Metal-carbon composite anode material and preparation method and application thereof
Technical Field
The invention relates to a high-capacity lithium ion battery negative electrode material and a preparation method thereof, belonging to the field of battery negative electrode materials.
Background
The lithium ion battery has a plurality of advantages in the aspects of energy density, cycle life, application range, safety, environmental protection and the like, and is an energy conversion and storage device with great development prospect at the present stage. The negative electrode material is one of the key factors affecting the overall performance thereof, and has been widely and intensively studied. The types of materials reported to be useful as negative electrode materials for lithium ion batteries include carbon materials, alloy materials, and metal oxide materials. The graphite carbon is a main commercial anode material, and has stable performance and lower specific capacity; the alloy anode material and the oxide anode material have the advantages of high theoretical capacity and good safety performance, and are novel anode materials with great potential, but repeated deintercalation of lithium ions can cause volume expansion and shrinkage of the materials, so that the materials are crushed and pulverized, and the problems of high first capacity loss, poor cycle stability, poor multiplying power discharge performance and the like of the battery are caused.
In order to solve the problems of alloy or metal oxide cathode materials, the prior art generally uses conductive carbon as a buffer framework, composites carbon with alloy or metal oxide, effectively buffers the existing volume expansion and improves the conductivity of the electrode, and improves the structural stability in the charge and discharge process. In addition, the problem of poor cycle performance caused by volume expansion of the material can be solved to a certain extent by nanocrystallizing or filming the material or preparing the three-dimensional porous material.
The patent CN10122344A disperses carbon nano-fibers in cobalt salt solution, and then adds alkali solution to obtain carbon nano-fiber-cobalt hydroxide compound, and the compound can be heat treated under a certain atmosphere to generate a composite anode material containing cobalt oxide. The patent CN104051718A mixes the chloride aqueous solution of tin with the transition metal cyanide aqueous solution, forms a tin-based cyanide gel system through sol-gel and freeze-drying processes, and uses the tin-based cyanide gel system as a precursor to perform heat treatment in air or oxygen atmosphere to obtain the three-dimensional nano porous tin dioxide-based composite oxide. Although the modification treatment of alloy or metal oxide anode materials in the prior literature or patent can effectively relieve the problems of poor conductivity and volume expansion and obtain improved electrochemical performance of the battery, the problems of complex preparation process, expensive raw materials, high production cost and the like exist, and the method is not suitable for practical production and application.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of a metal-carbon composite anode material.
The second object of the invention is to provide a metal-carbon composite anode material prepared by the preparation method.
A third object of the present invention is to provide the use of the composite anode material.
A preparation method of metal-carbon composite cathode material comprises mixing bituminous coal with metal source to obtain mixture; the mixture is sequentially subjected to primary sintering, secondary sintering and tertiary sintering; obtaining the composite anode material; wherein the temperature of the first-stage sintering is 300 ℃ or lower; the temperature of the second-stage sintering is 400-600 ℃; the temperature of the three-stage sintering is 700-1200 ℃.
The invention adopts bituminous coal as raw material; the raw material is matched with a metal source, and under the special three-stage sintering mechanism, the battery anode material with excellent electrical properties can be prepared.
Preferably, the bituminous coal is coking coal and/or fat coal.
The bituminous coal is preferably coking coal and/or fat coal in China coal Classification (GB/T5751-2009). Research shows that the electrical property of the prepared anode material is more excellent by adopting the preferred bituminous coal.
Preferably, the coking coal has the ash-free volatile content of 10% -28%, the bonding index of 50-65% and the maximum thickness of the colloid layer of less than or equal to 25%. The preferable oak expansion degree is less than or equal to 150 percent.
Further preferably, the coking coal has an ashless base volatile content of 15-25%, a bonding index of 55-60% and a maximum thickness of 15-20%.
Preferably, the fat coal comprises the components of 10-37% of ash-free volatile matter, the caking index is more than or equal to 85%, and the maximum thickness of the colloid layer is more than 25%.
Further preferably, the ash-free base volatile content of the fat coal is 20-30%, the bonding index is 90-95%, and the maximum thickness of the colloid layer is 30-40%.
Preferably, the bituminous coal contains at least one hetero element selected from nitrogen, sulfur and phosphorus. The use of bituminous coals containing the heteroatoms contributes to the production of anode materials with more excellent properties.
Preferably, in the bituminous coal, the total content of the hetero elements in the bituminous coal is not less than 2wt%; further preferably 4 to 10wt%.
Preferably, the bituminous coal is purified prior to sintering. Through purification treatment, the electrical property of the prepared anode material can be further improved.
Preferably, the ash content of the bituminous coal after the purification treatment is controlled to be less than or equal to 0.5%. The purified bituminous coal and the metal source are mixed and then subjected to the three-stage sintering, so that the performance of the prepared anode material is further improved.
In the invention, the method for purifying the bituminous coal can adopt the prior method, and the preferred purification treatment method adopted by the invention is an acid method or an alkali method.
Preferably, the acid method comprises the following steps: adding the dried, crushed and sieved bituminous coal into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1-1:10, regulating the total acid concentration to be 3-4, stirring and reacting for 2-5 hours at room temperature, filtering and washing to be neutral, and obtaining the bituminous coal purified by an acid method.
Preferably, the alkaline process comprises the following steps: adding the dried, crushed and screened bituminous coal into an aqueous solution of alkali metal hydroxide with the mass concentration of 7.5-17.5%, uniformly mixing, controlling the liquid-solid ratio to be 4-8, standing for 2-5 hours, drying in a drying oven at 105-120 ℃, roasting for 1-3 hours under the condition of 450-550 ℃ in an inert atmosphere, filtering and washing the roasted product to be neutral, and obtaining the bituminous coal purified by an alkaline method.
In the alkaline purification process, the aqueous solution of the alkali metal hydroxide is preferably an aqueous solution of sodium hydroxide.
Preferably, the metal source is at least one of an oxide, a salt and a hydroxide of a transition metal.
Further preferably, the transition metal is at least one of tin, antimony, cobalt, manganese, iron, titanium, chromium, nickel, and copper.
Preferably, the metal source is a water-soluble salt of the metal, preferably a chloride, nitrate, acetate, sulfate, or the like of the respective metal.
Preferably, the metal source is at least one of stannous chloride, antimony sulfate, antimony hydroxide, cobalt acetate, manganese nitrate, manganese acetate, ferric chloride, ferric sulfate, ferric nitrate, ferric hydroxide, titanium chloride, chromium chloride, nickel nitrate, nickel sulfate, copper chloride, copper sulfate and copper nitrate.
Mixing the bituminous coal or the purified bituminous coal with a metal source in a conventional manner, such as stirring, ball milling, ultrasonic dispersion, etc.; the ball-milling mixing is preferably wet ball-milling mixing.
Preferably, the mass ratio of the metal source to the bituminous coal is 1:20-20:1; further preferably, the ratio is 1:10 to 10:10.
In the present invention, it is preferable that bituminous coal and a metal source for oxidation treatment are sufficiently mixed in a solvent, and the mixed solution is dried to obtain the above-mentioned mixture.
The solvent is at least one of water, methanol, ethanol, propanol, toluene and diethyl ether.
In the present invention, the means for drying the mixed solution may be conventional methods. In the present invention, the mixture is preferably obtained by evaporating and drying the mixed solution.
Preferably, the mixed solution is continuously stirred for 2-12 hours at the temperature of 60-85 ℃ to enable moisture to be slowly evaporated to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 105-120 ℃ to be dried for 6-12 hours to obtain a uniform mixture of the metal oxide precursor and the bituminous coal.
In the invention, the sintering process is carried out under a protective atmosphere; preferably, the protective atmosphere is, for example, nitrogen and/or an inert gas; the inert gas is at least one of helium, argon and neon.
Preferably, the temperature of the primary sintering is 200-300 ℃.
Preferably, the sintering is carried out at the primary sintering temperature for 1-5h.
The temperature rising rate of the primary sintering is 1-10 ℃/min.
Preferably, the temperature of the two-stage sintering is 500-600 ℃.
Preferably, the sintering is carried out for 1-5h at the two-stage sintering temperature.
Preferably, the temperature of the three-stage sintering is 800-1000 ℃.
Preferably, the three-stage sintering temperature is used for heat preservation and sintering for 1-5h.
The temperature rising rate of the second-stage sintering and the third-stage sintering is 1-5 ℃/min.
Preferably, the sintered material is crushed and sieved to obtain the battery anode material.
The preparation method provided by the invention takes bituminous coal as a raw material, and is obtained through steps of crushing, screening, purifying, adding oxide precursors and three-stage pyrolysis. A preferred method for preparing a bituminous coal-based battery anode material comprises the steps of:
the first step: drying, crushing and screening bituminous coal as a raw material to obtain coal powder particles with the particle size below 20 microns;
and a second step of: purifying the bituminous coal particles obtained in the first step through an acid method or an alkali method to remove metal impurities in the bituminous coal, thereby obtaining purified bituminous coal with ash content less than 0.5%;
and a third step of: adding the purified bituminous coal in the second step into a solution containing a metal source according to the proportion of 1:20-20:1, continuously stirring for 2-12 hours at the temperature of 60-85 ℃ to enable moisture to evaporate slowly to form an adhesive, and then placing the adhesive in a drying oven at the temperature of 105-120 ℃ to dry for 6-12 hours to obtain a mixture;
fourth step: placing the mixture obtained in the step three into a sintering furnace which is filled with inert atmosphere, and sequentially carrying out primary sintering at 200-300 ℃, secondary sintering at 400-600 ℃ and tertiary sintering at 700-1200 ℃; and cooling to room temperature after sintering, taking out the sintered material, and crushing and grading the sintered material to obtain the composite anode material.
Preferably, in the first step, the drying temperature is 105-120 ℃ and the drying time is 10-12 hours, and the crushing mode is preferably that the crushing mode is that the vibrating crusher is used for crushing for 30s-5min and then the planetary ball mill is used for ball milling for 6-10 hours.
Preferably, in the third step, the inert atmosphere is at least one selected from helium, argon, neon and nitrogen, the heating system of the heat treatment of the third step is that the temperature is raised to 200-300 ℃ at the heating rate of 1-10 ℃/min, the temperature is kept for 1-5 hours, the temperature is raised to 400-600 ℃ at the heating rate of 1-5 ℃/min, the mixture is sintered for 1-5 hours, and finally the temperature is raised to 700-1200 ℃ at the heating rate of 1-5 ℃/min, and the mixture is sintered for 1-5 hours.
The invention also provides a composite anode material prepared by the preparation method.
The composite anode material comprises soft coal pyrolytic carbon; nano metal particles and/or nano metal oxide particles are distributed in the pyrolytic carbon of the bituminous coal.
The nano metal oxide is at least one of tin oxide, antimony oxide, cobalt oxide, manganese oxide, ferric oxide, titanium oxide, chromium oxide, nickel oxide, copper oxide and zinc oxide. The nanometer metal ions are corresponding simple substances obtained by in-situ reduction of metal oxides.
And the soft coal pyrolytic carbon is a product of sintering the soft coal through the first section, the second section and the third section.
Preferably, the particle size of the composite anode material is 5-25 microns.
Preferably, the composite anode material comprises soft coal pyrolytic carbon; nano metal particles and nano metal oxide particles are distributed in the pyrolytic carbon of the bituminous coal.
The preferred composite anode material consists of bituminous coal pyrolytic carbon, nano metal particles and nano metal oxide particles which provide high capacity, wherein the nano metal particles and the nano metal oxide particles are generated in situ in the bituminous coal pyrolytic carbon and are uniformly dispersed in the bituminous coal pyrolytic carbon, and a large number of holes and gaps exist in the bituminous coal pyrolytic carbon.
Preferably, the mass ratio of the soft coal pyrolytic carbon to the nano metal particles to the nano metal oxides of the composite anode material is 1:1:1-20: 1:20.
The invention also provides application of the composite anode material, which is used for preparing the anode of the lithium ion battery.
The composite anode material is preferably a lithium ion battery anode material.
In the invention, the negative electrode material of the battery can be used as a negative electrode active component to be assembled into the negative electrode of the lithium ion battery by adopting the existing method.
The invention has the principle and the characteristics that:
the soft coal has carbon content of 74-92%, volatile content of 18-26%, and contains a certain amount of N, P, S organic elements. In the pyrolysis process, a three-phase substance composition colloid body with gas-liquid-solid phase interpenetration can be formed, so that the carbon-metal oxide composite lithium ion battery anode material is prepared by utilizing a coking mechanism in the bituminous coal pyrolysis process. In the three-stage pyrolysis process, the first stage occurs at a lower temperature (room temperature-300 ℃) at which time the original molecular structure of the bituminous coal undergoes limited thermal action, mainly moisture removal, during which the oxide precursor crystallizes from the liquid phase and is stably dispersed among the bituminous coal particles; the second stage occurs at moderate temperature (about 500 ℃), at this time, the bituminous coal containing a suitable amount of colloid forms a viscous gas, liquid, solid three-phase coexisting mixture, and the added oxide precursor is easily and uniformly dispersed in the colloid liquid phase, and then melted and bonded to form semicoke containing the oxide precursor; through the third-stage pyrolysis (more than 700 ℃) at a higher temperature, the bituminous coal can undergo further polycondensation reaction to generate char with high carbon content, and meanwhile, the oxide precursor is thermally decomposed to form nano oxide. At higher temperature, the coal coke and the oxide react chemically to reduce part of the coal coke and the oxide into metal, and finally the high-capacity anode material consisting of the pyrolytic carbon of the bituminous coal, nano metal particles and nano oxide particles dispersed in the pyrolytic carbon of the bituminous coal is formed. So far, there are few reports on the preparation of high-capacity metal oxide anode materials for lithium ion batteries based on bituminous coal.
The invention has the beneficial effects that:
(1) Pyrolysis of the bituminous coal and pyrolysis of the oxide precursor synchronously occur, and oxidation-reduction reaction between a bituminous coal pyrolysis product and an oxide precursor pyrolysis product can occur to a certain extent, so that oxides and reduced metal products thereof can be uniformly dispersed in the bituminous coal pyrolytic carbon and can be tightly combined with a carbon shell layer.
(2) The soft coal pyrolytic carbon serves as a carbon skeleton, plays a role in separating oxide precursor particles, limits nucleation and growth of the precursor in the process of generating oxide and metal particles by the precursor, easily obtains non-agglomerated nano oxide and nano metal particles, and greatly relieves expansion effect in the charge and discharge process.
(3) The protective layer formed by the pyrolytic carbon of the bituminous coal can effectively improve the conductivity of the material and avoid the generation of a large amount of SEI films caused by direct contact of internal nano metal particles and nano oxide particles with electrolyte; in addition, the bituminous coal contains a certain amount of nitrogen, sulfur and phosphorus elements, so that in-situ doping is realized in the pyrolysis process, and the conductivity is further improved.
(4) In the pyrolysis process of the bituminous coal, volatile matters (high molecular organic matters) contained in the bituminous coal are decomposed vigorously at high temperature to generate and discharge a large amount of gaseous volatile matters, and a porous structure with a large amount of pore diameters and gaps can be formed in pyrolytic carbon of the bituminous coal, and the pore diameters and the gaps provide storage space for electrolyte, so that an ion transmission path is shortened, and the rate performance is improved.
(5) The obtained lithium ion battery anode material has high capacity, good rate capability and long cycle life; the bituminous coal has wide raw material sources and low cost; the preparation process is simple, easy to control and high in yield.
Drawings
FIG. 1 is an SEM image of a high capacity lithium ion battery anode material according to example 1 of the present invention
FIG. 2 is an XRD pattern of the negative electrode material of the high capacity lithium ion battery according to example 1 of the invention
It can be seen from fig. 1 that the metal oxide is uniformly dispersed in the pyrolysed carbon of the bituminous coal and is tightly combined with the carbon shell layer, and meanwhile, a large number of voids exist in the layer structure of the pyrolysed carbon of the bituminous coal.
As can be seen from fig. 2, the composite anode material formed by three-stage pyrolysis of oxide and carbon mainly contains two phases of manganese oxide and amorphous carbon.
Detailed description of the preferred embodiments
Example 1
(1) Selecting coking coal with 15% of ash-free volatile matter, 52% of bonding index and 25% of colloid layer maximum thickness, containing hetero atoms N, S, P and 4% of hetero atoms as raw materials, putting 100g of coking coal raw materials dried at 120 ℃ for 10 hours into a vibration pulverizer to crush for 1min, ball-milling for 6 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 4, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 2 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.37%.
(3) 10g of manganese acetate is dissolved in 100ml of water solution, 20g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 2 hours at the temperature of 60 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 6 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 200 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 1 ℃/min for 1 hour, heating to 500 ℃ at a heating rate of 1 ℃/min for 1 hour, sintering at 800 ℃ at a heating rate of 1 ℃/min for 1 hour, and taking out after cooling to room temperature. Crushing the sintered sample for 1min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Example 2
(1) Selecting coking coal with 25% of ash-free volatile matter, 62% of bonding index and 25% of colloid layer maximum thickness, containing hetero atoms N, S, P and 10% of hetero atoms as raw materials, putting 100g of coking coal raw materials dried at 120 ℃ for 12 hours into a vibration pulverizer to crush for 10 minutes, ball-milling for 10 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into a mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 2:1, the liquid-solid ratio is 6, the total acid concentration is regulated to pH value of 4, stirring reaction is carried out for 5 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.42%.
(3) 20g of manganese acetate is dissolved in 100ml of water solution, 1g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 12 hours at the temperature of 85 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 12 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) And placing 10g of the dried mixture into a graphite ark, heating to 300 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 5 ℃/min, preserving heat for 5 hours, heating to 600 ℃ at a heating rate of 5 ℃/min, sintering for 5 hours, heating to 1000 ℃ at a heating rate of 5 ℃/min, sintering for 5 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 5min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Example 3
(1) Selecting coking coal with 20% of ashless base volatile content, 58% of bonding index and 18% of colloid layer maximum thickness and containing N, S, P of hetero atoms and 8% of hetero atoms as raw materials, putting 100g of bituminous coal raw materials dried at 105 ℃ for 10 hours into a vibration pulverizer to crush for 5 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 5, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 5 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.23%.
(3) 10g of manganese acetate is dissolved in 100ml of water solution, 50g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 6 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 105 ℃ to be dried for 10 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 250 ℃ at a heating rate of 3 ℃/min in a muffle furnace protected by nitrogen atmosphere, preserving heat for 3 hours, heating to 550 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Example 4
(1) Selecting fat coal with 25% of ash-free volatile matter, a bonding index of 95%, a maximum thickness of a colloid layer of 35%, and a heteroatom N, S, P and a heteroatom content of 8% as raw materials, putting 100g of the fat coal raw materials dried at 105 ℃ for 10 hours into a vibration pulverizer to crush for 4 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of fertilizer coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 6, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining fertilizer coal after acid purification, and ash content of the fertilizer coal after purification is 0.33%.
(3) 10g of stannous chloride is dissolved in 100ml of water solution, 50g of purified fat coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 10 hours, so that a uniform mixture of a metal oxide precursor and the fat coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 250 ℃ at a heating rate of 3 ℃/min in a muffle furnace protected by nitrogen atmosphere, preserving heat for 3 hours, heating to 550 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the fertilizer coal-based battery anode material with the average particle size of 18 microns.
Example 5
(1) Selecting coking coal with 20% of ash-free volatile matter, 58% of adhesive index and 18% of colloid layer maximum thickness, wherein the heteroatom N, S, P and heteroatom content 8% of coking coal are used as raw materials, 100g of coking coal raw material dried at 120 ℃ for 12 hours is put into a vibration pulverizer to be crushed for 5min, and then is ball-milled for 8 hours by a planetary ball mill, and screening is carried out by a 500-mesh sieve, so as to obtain undersize.
(2) 50g of dried, crushed and screened coking coal is added into 10 percent sodium hydroxide aqueous solution and mixed uniformly, the liquid-solid ratio is controlled at 6, the coking coal is dried in a drying box at 120 ℃ after standing for 4 hours, then the coking coal is roasted for 3 hours under the condition of 500 ℃ in inert atmosphere, the roasted product is filtered and washed to be neutral, the bituminous coal purified by an alkaline method is obtained, and the ash content of the bituminous coal after purification is 0.47 percent.
(3) 10g of stannous chloride is dissolved in 100ml of water solution, 50g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 10 hours, so that a uniform mixture of a metal oxide precursor and bituminous coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 300 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 3 ℃/min for 3 hours, heating to 600 ℃ at a heating rate of 3 ℃/min for 3 hours, heating to 900 ℃ at a heating rate of 5 ℃/min for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 5min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Example 6:
1) Selecting coking coal with 15% of ash-free base volatile component, 58% of bonding index and 25% of colloid layer maximum thickness as raw materials, wherein the heteroatom N, S, P and heteroatom content 8% of coking coal are contained, putting 100g of coking coal raw materials dried at 120 ℃ for 10 hours into a vibration pulverizer to crush for 5 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 6, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.22%.
(3) 10g of stannous chloride is dissolved in 100ml of water solution, 50g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 10 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 250 ℃ at a heating rate of 3 ℃/min in a muffle furnace protected by nitrogen atmosphere, preserving heat for 3 hours, heating to 550 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Comparative example 1
Anthracite coal is adopted in the comparative example, and the specific operation is as follows:
(1) Anthracite with 6.9 percent of dry ash-free radical volatile content and 4 percent of dry ash-free radical hydrogen content is taken as a raw material, 100g of anthracite raw material dried for 12 hours at 120 ℃ is put into a vibration pulverizer to be crushed for 5 minutes, and then is ball-milled for 8 hours by a planetary ball mill, and is sieved by a 500-mesh sieve, and the undersize is taken.
(2) 50g of anthracite after drying, crushing and screening is added into a mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 6, the total acid concentration is regulated to be 3, the stirring reaction is carried out for 4 hours at room temperature, the anthracite after purification by an acid method is obtained after filtration and washing to be neutral, and the ash content of the anthracite after purification is 0.24%.
(3) 10g of manganese acetate is dissolved in 100ml of water solution, 50g of purified anthracite is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 6 hours, so that a uniform mixture of a metal oxide precursor and the anthracite is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 200 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 5 ℃/min for 3 hours, heating to 500 ℃ at a heating rate of 5 ℃/min for 3 hours, heating to 900 ℃ at a heating rate of 5 ℃/min for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the anthracite-based battery anode material with the average particle size of 18 microns.
Comparative example 2:
the comparative example discusses the use of lignite, and the specific operation is as follows:
1) Selecting brown coal with ash-free base volatile content of 40%, heteroatom N, S, P and heteroatom content of 6% as raw materials, putting 100g of brown coal raw materials dried at 120 ℃ for 10 hours into a vibration pulverizer, pulverizing for 5 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of lignite after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 6, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, lignite purified by an acid method is obtained, and the ash content of the lignite after purification is 0.22%.
(3) 10g of manganese acetate is dissolved in 100ml of water solution, 50g of purified lignite is added for ultrasonic dispersion for 3 hours, the mixed material is continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 10 hours, so that a uniform mixture of a metal oxide precursor and lignite is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 250 ℃ at a heating rate of 3 ℃/min in a muffle furnace protected by nitrogen atmosphere, preserving heat for 3 hours, heating to 550 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the secondarily crushed sample to obtain the lignite-based battery anode material with the average particle size of 18 microns.
Comparative example 3
The three-stage calcination mechanism required by the invention is not adopted in the discussion of the comparative example, and the specific operation is as follows:
(1) Selecting coking coal with 20% of ash-free volatile matter, 58% of adhesive index and 18% of colloid layer maximum thickness, containing hetero atoms N, S, P and 8% of hetero atoms as raw materials, putting 100g of coking coal raw materials dried at 120 ℃ for 12 hours into a vibration pulverizer to crush for 5min, ball-milling for 8 h by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 5, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.23%.
(3) 10g of manganese acetate is dissolved in 100m1 of aqueous solution, 50g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 6 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) 10g of the dried mixture is placed in a graphite ark, heated to 1000 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 5 ℃/min, kept for 3 hours, cooled to room temperature and taken out. Crushing the sintered sample for 5min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Comparative example 4
The comparative example was discussed without the addition of an oxide precursor, and the specific procedure was as follows:
(1) Selecting coking coal with 20% of ash-free volatile matter, 58% of adhesive index and 18% of colloid layer maximum thickness, containing hetero atoms N, S, P and 8% of hetero atoms as raw materials, putting 100g of coking coal raw materials dried at 120 ℃ for 12 hours into a vibration pulverizer to crush for 5min, ball-milling for 8 h by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, the liquid-solid ratio is 5, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining coking coal after acid purification, and ash content of the coking coal after purification is 0.22%.
(3) Dissolving 10g of purified coking coal in 100ml of aqueous solution, performing ultrasonic dispersion for 3 hours, continuously stirring at 70 ℃ for 4 hours after uniform dispersion, slowly evaporating water to form an adhesive body, and then placing the adhesive body in a drying oven at 120 ℃ for drying for 6 hours to obtain a uniformly mixed solid coking coal material.
(4) Placing 10g of dried mixture into a graphite ark, heating to 200 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 5 ℃/min for 3 hours, heating to 500 ℃ at a heating rate of 5 ℃/min for 3 hours, heating to 900 ℃ at a heating rate of 5 ℃/min for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 5min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
Comparative example 5
The comparative example discusses that the content of hetero atoms in raw coking coal is less, and the specific operation is as follows:
(1) Selecting coking coal with 22% of ash-free volatile matter, 60% of bonding index and 20% of colloid layer maximum thickness, wherein the heteroatom N, S, P and heteroatom content 1% of coking coal are used as raw materials, putting 100g of coking coal raw materials dried at 120 ℃ for 12 hours into a vibration pulverizer to crush for 5 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize.
(2) 50g of coking coal after drying, crushing and screening is added into hydrofluoric acid and sulfuric acid with the mass ratio of 10:1, the liquid-solid ratio is 5, the total acid concentration is regulated to pH value of 3, stirring reaction is carried out for 4 hours at room temperature, filtering and washing are carried out to neutrality, thus obtaining the coking coal purified by an acid method, and the ash content of the coking coal after purification is 0.22%.
(3) 10g of manganese acetate is dissolved in 100ml of water solution, 50g of purified coking coal is added for ultrasonic dispersion for 3 hours, the mixed materials are continuously stirred for 8 hours at the temperature of 70 ℃ to enable moisture to be evaporated slowly to form an adhesive body, and then the adhesive body is placed in a drying oven at the temperature of 120 ℃ to be dried for 6 hours, so that a uniform mixture of a metal oxide precursor and the coking coal is obtained.
(4) Placing 10g of dried mixture into a graphite ark, heating to 200 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 5 ℃/min for 3 hours, heating to 500 ℃ at a heating rate of 5 ℃/min for 3 hours, heating to 900 ℃ at a heating rate of 5 ℃/min for 3 hours, and taking out after cooling to room temperature. Crushing the sintered sample for 5min by a vibration crusher for secondary crushing, and then carrying out multistage vibration screening on the sample after secondary crushing to obtain the coking coal-based battery anode material with the average particle size of 18 microns.
The electrical properties of each of the examples and comparative examples were measured as follows:
(1) The preparation process of the electrode comprises the following steps: the prepared active material, PVDF and conductive carbon black (acetylene black) are mixed in a mass ratio of 8:1:1, and a certain amount of N-methylpyrrolidone (NMP) is added, and the mixture is fully and uniformly mixed in an agate mortar. And uniformly coating the uniformly mixed slurry on the copper foil, and drying the copper foil coated with the slurry in a vacuum drying oven at 120 ℃ for 12 hours after the coating is finished. After the drying is finished, the electrode slice is cut into a wafer with the diameter of 12mm, and then the electrode slice is weighed and marked, dried and placed in a glove box for standby.
(2) The battery assembly process comprises the following steps: in the experiment, button type half batteries are adopted to test the electrochemical performance of the material, all battery assembly is carried out in a glove box under the argon atmosphere, the water oxygen value detection is required to be always less than 0.1ppm in the assembly process, and the commercial 1mol L electrolyte is adopted in the assembly process -1 Lithium hexafluorophosphate of (2)The electrolyte is used as lithium ion battery electrolyte, a polypropylene (PP) diaphragm is used as a diaphragm of the lithium ion battery, and the lithium ion battery takes a lithium sheet as a counter electrode; all cells were assembled into 2025 coin cells and sealed with a battery sealer in a glove box. The battery is assembled in the order of the negative electrode shell, the pole piece electrolyte, the diaphragm, the electrolyte, the lithium piece, the nickel piece and the positive electrode shell.
The test results are shown in Table 1:
table 1 results of electrochemical performance test in lithium half batteries of examples 1 to 5 and comparative examples 1 to 5
From the results of the electrochemical performance test, examples 1 to 6 have good overall electrochemical performance.
In comparative example 1, anthracite is used as a raw material, so that the volatile components are too low, the quantity of colloid is small, the fluidity is poor in the high-temperature heat treatment process, and the adhesion is avoided, so that the added nano oxide cannot be dispersed in the anthracite, an effective conductive framework cannot be formed, and the electrochemical performance is poor.
In comparative example 2, brown coal is used as a raw material, so that the volatile component is too high, expansion occurs in the high-temperature heat treatment process, the coking performance of the material is also poor, and a uniformly-coated nano metal oxide/carbon composite anode material cannot be formed, so that the electrochemical performance is influenced.
In comparative example 3, three-stage pyrolysis is not adopted, so that the coking speed of coking coal is difficult to control in the pyrolysis process, and the obtained pyrolytic carbon is difficult to uniformly coat nano metal oxide, so that the electrochemical performance is poor.
In comparative example 4, since the oxide precursor was not added, high capacity oxide and reduced metal particles could not be formed in the anode material, and thus the capacity was low.
In comparative example 5, since the heteroatom content in the coking coal is low, and the ash-free volatile content, the caking index, and the maximum thickness of the mass layer of the coking coal are outside the preferred ranges, it is impossible to produce uniformly coated nano metal oxide in the anode material and provide good conductivity, and thus the electrochemical performance is poor.

Claims (8)

1. A preparation method of a metal-carbon composite anode material for a lithium ion battery is characterized in that bituminous coal and a metal source are mixed to obtain a mixture; the mixture is sequentially subjected to primary sintering, secondary sintering and tertiary sintering; obtaining the composite anode material for the lithium ion battery; the composite anode material comprises soft coal pyrolytic carbon; nano metal oxide particles or composite particles of nano metal oxide particles are distributed in the pyrolytic carbon of the bituminous coal; wherein the nano metal oxide is at least one of tin oxide, antimony oxide, cobalt oxide, manganese oxide, ferric oxide, titanium oxide, chromium oxide, nickel oxide, copper oxide and zinc oxide; the nano metal ions are corresponding simple substances obtained by in-situ reduction of metal oxides;
the sintering process is carried out under a protective atmosphere; wherein the temperature of the first-stage sintering is 300 ℃ or lower; the temperature of the second-stage sintering is 400-600 ℃; the temperature of the three-stage sintering is 700-1200 ℃; the protective atmosphere is nitrogen and/or inert gas;
the bituminous coal is coking coal and/or fat coal;
the ash-free volatile content of the coking coal is 10-28%, the bonding index is 50-65, and the maximum thickness of a colloid layer is less than or equal to 25mm;
the components of the fat coal are that the ash-free base volatile content is 10-37%, the bonding index is more than or equal to 85, and the maximum thickness of a colloid layer is more than 25mm;
the bituminous coal contains at least one of nitrogen, sulfur and phosphorus; the total content of the hetero elements in the bituminous coal is not less than 2wt%;
the bituminous coal is purified before sintering, and ash content of the bituminous coal after the purification treatment is controlled to be less than or equal to 0.5%;
the purification treatment method is an acid method or an alkali method; wherein, the liquid crystal display device comprises a liquid crystal display device,
the acid method comprises the following steps: adding the dried, crushed and sieved bituminous coal into a mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1-1:10, regulating the total acid concentration to be 3-4, stirring at room temperature for reaction for 2-5 hours, filtering and washing to be neutral to obtain the bituminous coal purified by an acid method;
the alkaline method comprises the following steps: adding the dried, crushed and screened bituminous coal into an alkali metal hydroxide aqueous solution with the mass concentration of 7.5-17.5%, uniformly mixing, controlling the liquid-solid ratio to be 4-8, standing for 2-5 hours, drying in a drying box at 105-120 ℃, roasting for 1-3 hours at 450-550 ℃ in an inert atmosphere, filtering and washing the roasted product to be neutral, and thus obtaining the bituminous coal purified by an alkaline method.
2. The method according to claim 1, wherein the metal source is at least one of an oxide, a salt, and a hydroxide of a transition metal; the transition metal is at least one of tin, antimony, cobalt, manganese, iron, titanium, chromium, nickel and copper.
3. The method of claim 1, wherein the bituminous coal is mixed with a metal source in a solvent to obtain a mixed solution; evaporating and drying the mixed solution to obtain the mixture;
the solvent is at least one of water, methanol, ethanol, propanol, toluene and diethyl ether.
4. The method of claim 3, wherein the mass ratio of metal source to bituminous coal is 1:20 to 20:1.
5. The method according to claim 1, wherein the sintering is carried out at the one-stage sintering temperature for 1 to 5 hours; heat preservation and sintering are carried out for 1-5h at the two-stage sintering temperature; and (3) heat preservation and sintering for 1-5h at the three-stage sintering temperature.
6. The method of manufacturing of claim 1, wherein the steps include:
(1) Selecting coking coal with 20% of ash-free volatile matter and a bonding index of 58 and a maximum thickness of a colloid layer of 18mm and containing hetero atoms N, S, P and 8% of hetero atoms as raw materials, putting 100g of bituminous coal raw materials dried at 105 ℃ for 10 hours into a vibration pulverizer to crush for 5 minutes, ball-milling for 8 hours by a planetary ball mill, screening by a 500-mesh sieve, and taking undersize;
(2) Adding 50g of coking coal subjected to drying, crushing and screening into a mixed acid solution with the mass ratio of hydrofluoric acid to sulfuric acid of 10:1, wherein the liquid-solid ratio is 5, regulating the total acid concentration to pH value to 3, stirring at room temperature for reaction for 5 hours, filtering and washing to neutrality to obtain coking coal subjected to acid purification, and the ash content of the coking coal after purification is 0.23%;
(3) Dissolving 10g of manganese acetate in 100ml of aqueous solution, adding 50g of purified coking coal, performing ultrasonic dispersion for 3 hours, continuously stirring the mixed material at the temperature of 70 ℃ for 6 hours, slowly evaporating water to form an adhesive, and then placing the adhesive in a 105 ℃ drying oven for drying for 10 hours to obtain a uniform mixture of a metal oxide precursor and the coking coal;
(4) Placing 10g of dried mixture into a graphite ark, heating to 250 ℃ in a muffle furnace protected by nitrogen atmosphere at a heating rate of 3 ℃/min for 3 hours, heating to 550 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, sintering for 3 hours, and taking out after cooling to room temperature; crushing the sintered sample for 3min by a vibration crusher for secondary crushing, and then performing multistage vibration screening on the secondarily crushed sample to obtain a coking coal-based battery anode material with an average particle size of 18 microns;
the battery cathode material contains two phases of manganese oxide and amorphous carbon.
7. A composite anode material produced by the production method of any one of claims 1 to 6; the method is characterized by comprising the steps of pyrolyzing carbon by bituminous coal; nano metal oxide particles or composite particles containing nano metal oxide particles and nano metal particles are distributed in the pyrolytic carbon of the bituminous coal.
8. Use of the composite negative electrode material according to claim 7 for the preparation of a negative electrode for a lithium ion battery.
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