CN110190252B - Metal lithium-carbon composite material and preparation method thereof - Google Patents

Metal lithium-carbon composite material and preparation method thereof Download PDF

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CN110190252B
CN110190252B CN201910386497.8A CN201910386497A CN110190252B CN 110190252 B CN110190252 B CN 110190252B CN 201910386497 A CN201910386497 A CN 201910386497A CN 110190252 B CN110190252 B CN 110190252B
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carbon
composite material
metal lithium
lithium
carbon composite
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CN110190252A (en
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杨书廷
孙志贤
王秋娴
岳红云
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Battery Research Institute Of Henan Co ltd
Henan Normal University
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Henan Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a metal lithium-carbon composite material, which comprises a spherical or sphere-like carrier of carbon and metal lithium formed in pores of the spherical or sphere-like carrier of the carbon, wherein the spherical or sphere-like carrier of the carbon is formed by aggregating partially graphitized nano-based carbon materials. The invention also discloses a preparation method of the metal lithium-carbon composite material, which comprises the steps of dissolving the nano conductive carbon material, the surfactant and the soluble transition metal salt in water, and then spraying and drying to obtain a precursor; carbonizing the precursor to obtain carbon spheres; and (3) washing the carbon spheres with water after acid washing until the carbon spheres are neutral, and then co-melting the carbon spheres with metal lithium in an argon atmosphere to obtain the metal lithium-based composite negative electrode material. According to the local graphitized metal lithium-carbon composite material, in the charging and discharging processes of the battery, the graphitized parts which are orderly and uniformly distributed guide the deposition of the metal lithium to be more uniform, so that the generation of lithium dendrites is reduced, and the cycle life of a metal lithium cathode is prolonged.

Description

Metal lithium-carbon composite material and preparation method thereof
Technical Field
The invention relates to a lithium ion battery cathode material, in particular to a metal lithium-carbon composite material and a preparation method thereof.
Background
The importance of the energy storage technology in the current society is more and more prominent, and the application of the energy storage technology is more and more inexistent in the fields of large-scale storage of clean energy such as light energy, wind energy, tidal energy and the like, large-scale power grid peak regulation, transportation, portable equipment, special operation and the like. The lithium ion battery system has the advantages of high energy density, long cycle life, flexible structural design and the like, and is applied to transportation and portable equipment on a large scale. The traditional lithium ion battery system taking lithium iron phosphate, ternary materials and the like as the anode and graphite materials as the cathode has the mass energy density close to the theoretical limit, and the increasing speed of the energy density cannot adapt to the increase of social demands. The state is definitely proposed in white paper of 2025 manufactured by China that the energy density of the power battery in China is 300wh/kg, 400wh/kg in 2025 and 500wh/kg in 2030 by 2020. To increase energy mass energy density, the architecture of the battery must be revolutionarily modified. In the lithium ion battery, the metal lithium-based material is taken as the negative electrode, so that the capacity of the lithium-containing positive electrode material can be fully exerted, and a high-capacity positive electrode which does not contain lithium, such as a sulfur-carbon composite material and the like, can be used. In addition, the metal lithium-based material cathode can obviously reduce the mass of the cathode, thereby improving the overall mass energy density of the battery.
However, in the lithium ion battery system in the prior art, when the metal lithium is directly used as the negative electrode, lithium dendrite is generated due to the irregular deposition of the metal lithium ions, so that the cycle life of the metal lithium negative electrode is greatly shortened, and the safety performance of the battery is reduced.
In the prior art, a metal lithium-carbon composite negative electrode material is prepared by melting a skeleton carbon sphere and metal lithium by using a spray drying method, but the deposition of the metal lithium is not controlled and guided, so that the deposition of the lithium is disordered and the distribution of the lithium is not uniform.
Disclosure of Invention
The invention aims to provide a metal lithium-carbon composite material with orderly deposited and uniformly distributed metal lithium and a preparation method thereof.
The technical scheme of the invention is as follows:
the invention provides a metal lithium-carbon composite material, which comprises a spherical or sphere-like carrier of carbon and metal lithium formed in pores of the spherical or sphere-like carrier of the carbon, wherein the spherical or sphere-like carrier of the carbon is formed by aggregating nano-based carbon materials, and the nano-based carbon materials are partially graphitized.
The invention also provides a preparation method of the metal lithium-carbon composite material, which comprises the following steps:
the method comprises the following steps: dissolving a nano conductive carbon material, a high molecular surfactant and a soluble transition metal salt in water, and then carrying out spray drying to obtain a precursor;
step two: carbonizing the precursor to obtain carbon spheres;
step three: washing the carbon spheres with water to neutrality after acid washing;
step four: and co-melting the carbon spheres and the metal lithium in an argon atmosphere to obtain the metal lithium-carbon composite material.
In the invention, the soluble salt of the transition metal is dissolved in water and then uniformly added into the nano-carbon material to form a precursor, the transition metal salt is reduced into a transition metal simple substance by carbon during carbonization treatment of the precursor, and the transition metal simple substance is used as a catalyst for carbon graphitization when further carbonization is continued, so that the nano-base carbon material is graphitized at a position with the transition metal. Due to the ordered and uniform distribution of the soluble transition metal salt in the nano-carbon material, the distribution of the graphitized parts is relatively ordered and uniform.
In the charging and discharging process of the battery, because the lithium intercalation potential of the graphitized carbon is higher than that of the metal lithium, the metal lithium is firstly deposited on the surface of the graphitized carbon which is uniformly distributed, so that the deposition of the metal lithium is effectively guided to be more uniform, and the generation of lithium dendrites is reduced.
Preferably, the carbonization treatment is heating to 1000 ℃ in a nitrogen atmosphere and keeping the temperature for 1-12 h; more preferably, the carbonization treatment is heating to 800 ℃ in a nitrogen atmosphere and holding for 6 hours.
Preferably, the nano conductive carbon material is carbon nanotube, nano carbon fiber, graphene or ketjen black.
Preferably, the polymeric surfactant is polyvinylpyrrolidone, cationic starch, carboxymethyl cellulose or hydroxypropyl cellulose.
Preferably, the water-soluble transition metal salt is an iron salt, a cobalt salt or a nickel salt. Further, the ferric salt is ferric nitrate or ferric sulfate; the cobalt salt is cobalt chloride or cobalt sulfate; the nickel salt is nickel nitrate, nickel sulfate or nickel acetate.
Preferably, the temperature of an air inlet of the spray drying is 105-300 ℃, the air inlet pressure is 0.2-0.6 MPa, and the feeding speed is 3-15 ml/min.
The invention has the beneficial effects that:
the carbon spherical or sphere-like carrier of the metal lithium-carbon composite material is formed by aggregating nano-base materials, and the nano-base carbon material is locally graphitized and has good conductivity, rich pore structure and higher specific surface area. In the charging and discharging process of the battery, the ordered and uniformly distributed graphitized parts guide the deposition of the metal lithium to be more uniform, so that the generation of lithium dendrites is reduced, the cycle life of a metal lithium cathode is prolonged, and meanwhile, the utilization rate of the metal lithium is improved by virtue of the abundant pore structure and the three-dimensional conductive network, so that the energy density of the battery is improved.
Drawings
FIG. 1 is a TEM image of the lithium-carbon composite material prepared by the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto.
Example 1
70g of cationic starch and 30g of Ni (CH)3COO)2·4H2O is dissolved in 500ml of deionized water and stirred until completely dissolved, thus obtaining a green solution. 30g of Ketjen black was added and mechanically stirred at 500rpm for 12 hours, during which time it was dispersed for 6 hours using an ultrasonic disperser to obtain a uniformly dispersed black slurry. And (3) carrying out spray drying on the black slurry, wherein the temperature of an air inlet of spray is 105 ℃, the air inlet pressure is 0.2MPa, and the feeding rate is 3ml/min, so as to obtain precursor powder.
Putting the precursor powder into a tube furnace, introducing nitrogen atmosphere, heating to 1000 ℃, and keeping the temperature for 1h to obtain the nano-micro structureThe partially graphitized carbon spheres of (1). During this carbonization process, cationic starch becomes amorphous carbon, Ni, upon carbonization2+The carbon is reduced into simple substance nickel, and the nickel simple substance is used as a catalyst for graphitizing the amorphous carbon in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the position with the metal simple substance nickel. Due to cationic starch and soluble Ni (CH)3COO)2·4H2Dissolving O in water, adding nanometer carbon material Keqin black, and dispersing to obtain Ni (CH)3COO)2Ni in (1) 2+Ordered and uniform distribution is formed in the cationic starch, and then the cationic starch is ordered and uniformly distributed after being carbonized into amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniformly distributed.
Dispersing the carbon spheres in 2M HNO3And carrying out reflux heating at 120 ℃ for 12h for acid washing, then filtering, washing the carbon spheres with deionized water to be neutral, and carrying out vacuum drying for 24 h. In the process, as the metallic nickel simple substance is corroded in the acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) putting 4g of the carbon spheres and 6g of the metal lithium into a reaction kettle under the protection of argon, heating to 200 ℃, and preserving the temperature for 20min to obtain the material, namely the metal lithium-carbon composite negative electrode material.
FIG. 1 is a TEM image of the lithium-carbon composite material prepared in this example, wherein the SEM is JEM-2100, the test accelerating voltage is 200KV, and the discharge rate is 8000. As can be seen from fig. 1, the portion shown in the white box in the figure has a partially graphitized shadow of the nano-based carbon material in the lithium-carbon composite. From the figure, it can be seen that the nano-based carbon material graphitized sites in the lithium-carbon composite material are uniformly and orderly distributed.
And (3) testing electrical properties:
the prepared metal lithium-carbon composite material is used as a lithium ion battery negative electrode material to prepare a soft package battery, and the battery system is as follows: the positive electrode comprises lithium iron phosphate, polyvinylidene fluoride, Super P and carbon nano tubes in a mass ratio of 90:2:4:4, and the surface density of the positive electrode active material is 10mg/cm2(ii) a LiPF with 1M lithium salt electrolyte6The solvent is a solvent with the volume ratio of 1: 1 ethylene carbonate and dimethyl carbonate. The battery is charged and discharged at 0.1C, and the capacity retention rate of the battery is 89% after 100 cycles.
Example 2
50g of carboxymethylcellulose and 20g of Fe (NO)3)3·9H2O is dissolved in 700ml of deionized water and is stirred by magnetic force until the O is completely dissolved, so that yellow clear transparent solution is obtained. After 50g of Ketjen black was added, it was mechanically stirred at 500rpm for 12 hours, during which it was dispersed for 6 hours using an ultrasonic disperser, to obtain a uniformly dispersed black slurry. And (3) carrying out spray drying on the black slurry, setting the temperature of an air inlet to be 200 ℃, the air inlet pressure to be 0.6MPa and the feeding rate to be 15ml/min, and obtaining precursor powder.
And (3) putting the precursor powder into a tubular furnace, introducing nitrogen atmosphere, heating to 800 ℃, and keeping the temperature for 6h to obtain the partially graphitized carbon spheres with the nano-micro structure. During this carbonization process, carboxymethyl cellulose becomes amorphous carbon, Fe, upon carbonization3+The carbon is reduced into simple substance iron, the iron simple substance is used as a catalyst for graphitizing the amorphous carbon in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the part with the metal simple substance iron. Due to carboxymethyl cellulose and Fe (NO)3)3·9H2Dissolving O in water, adding Ketjen black, and dispersing to obtain Fe (NO)3)3Fe in (1)3+Ordered and uniform distribution is formed in the carboxymethyl cellulose, and then the carboxymethyl cellulose is orderly and uniformly distributed after being carbonized into the amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniformly distributed.
Dispersing the carbon spheres in 2M HNO3And carrying out reflux heating at 120 ℃ for 12h for acid washing, then filtering, washing the carbon spheres with deionized water to be neutral, and carrying out vacuum drying for 24 h.In the process, as the metallic iron simple substance is corroded in the pickling process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) placing 5g of the carbon spheres and 5g of the lithium metal into a reaction kettle under the protection of argon, heating to 200 ℃, and preserving heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
Using the same battery system and test method as in example 1, charge and discharge cycles were performed 100 times, and the battery capacity retention ratio was 95.3%.
Example 3
30g of hydroxypropyl cellulose and 15g of CoSO4·7H2O is dissolved in 800ml of deionized water and is stirred by magnetic force until the O is completely dissolved, so that red clear and transparent solution is obtained. 70g of carbon nanofibers are added and mechanically stirred for 12 hours at the rotating speed of 500rpm, and the mixture is dispersed for 6 hours by using an ultrasonic disperser, so that uniformly dispersed black slurry is obtained. And (3) carrying out spray drying on the black slurry, setting the temperature of an air inlet to be 300 ℃, the air inlet pressure to be 0.4MPa and the feeding rate to be 9ml/min, and obtaining precursor powder.
And (3) putting the precursor powder into a tube furnace, introducing nitrogen atmosphere, heating to 500 ℃, and preserving heat for 12h to obtain the partially graphitized carbon ball with the nano-micro structure. During this carbonization process, hydroxypropyl cellulose becomes amorphous carbon, Co, when carbonized2+The carbon is reduced into simple substance cobalt, the simple substance cobalt is used as a catalyst for graphitizing the amorphous carbon in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the position with the metal simple cobalt. Due to the hydroxypropyl cellulose and the soluble CoSO4·7H2O is dissolved in water, and then nano carbon fiber is added to be uniformly dispersed, so that CoSO4Of (5) Co2+Form an ordered and uniform distribution in the hydroxypropyl cellulose and further a full and uniform distribution after the carbonization of the hydroxypropyl cellulose into amorphous carbon, such thatThe site distribution of amorphous carbon graphitization is also relatively ordered and uniform.
Dispersing the carbon spheres in 2M HNO3And carrying out reflux heating at 120 ℃ for 12h for acid washing, then filtering, washing the carbon spheres with deionized water to be neutral, and carrying out vacuum drying for 24 h. In the process, as the metallic cobalt simple substance is corroded in the acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) placing 3g of the carbon spheres and 7g of the lithium metal into a reaction kettle under the protection of argon, heating to 200 ℃, and preserving heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
The same battery system and test method as in example 1 were used, and charge and discharge cycles were performed 100 times, and the battery capacity retention ratio was 92.6%.
Example 4:
10g of polyvinylpyrrolidone and 6g of Ni (NO)3)2·6H2Dissolving O in 1000ml of deionized water, and magnetically stirring until the O is completely dissolved to obtain a green clear transparent solution. 90g of graphene is added and mechanically stirred for 12h at the rotating speed of 500rpm, and the mixture is dispersed for 6h by using an ultrasonic disperser, so that uniformly dispersed black slurry is obtained. And (3) carrying out spray drying on the black slurry, setting the temperature of an air inlet to be 200 ℃, the air inlet pressure to be 0.4MPa and the feeding rate to be 6ml/min, and obtaining precursor powder.
And (3) putting the precursor powder into a tube furnace, introducing nitrogen atmosphere, heating to 800 ℃, and preserving heat for 2h to obtain the partially graphitized carbon spheres with the nano-micro structure. During this carbonization process, polyvinylpyrrolidone becomes amorphous carbon, Ni, upon carbonization2+The carbon is reduced into simple substance nickel, and the nickel simple substance is used as a catalyst for graphitizing the amorphous carbon in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the position with the metal simple substance nickel. The polyvinylpyrrolidone and soluble Ni (N)O3)2·6H2O is dissolved in water, and then nano carbon material graphene is added to be uniformly dispersed, so that Ni (NO)3)2Ni in (1)2+Ordered and uniform distribution is formed in the polyvinylpyrrolidone, and then the polyvinylpyrrolidone is ordered and uniformly distributed after being carbonized into amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniformly distributed.
Dispersing the carbon spheres in 2M HNO3And refluxing and heating at 120 ℃ for 12h for acid washing, then filtering, washing carbon spheres with deionized water to be neutral, and then drying in vacuum for 24 h. In the process, as the metallic nickel simple substance is corroded in the acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) putting 8g of the carbon spheres and 2g of the lithium metal into a reaction kettle protected by argon, setting the temperature to be 200 ℃, and preserving the heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
Using the same battery system and test method as in example 1, charge and discharge cycles were performed 100 times, and the battery capacity retention rate was 91.8%.
Example 5:
50g of polyvinylpyrrolidone and 5g of FeSO4·7H2O is dissolved in 1000ml of deionized water, and the mixture is magnetically stirred until the O is completely dissolved, so that a green solution is obtained. 50g of carbon nanotubes were added and mechanically stirred at 500rpm for 12 hours, during which time they were dispersed for 6 hours using an ultrasonic disperser to obtain a uniformly dispersed black slurry. And (3) carrying out spray drying on the black slurry, setting the temperature of an air inlet to be 200 ℃, the air inlet pressure to be 0.4MPa and the feeding rate to be 6ml/min, and obtaining precursor powder.
And (3) putting the precursor powder into a tubular furnace, introducing nitrogen atmosphere, heating to 800 ℃, and preserving heat for 2h to obtain the partially graphitized carbon spheres with the nano-micro structure. In the process of carbonizationPolyvinylpyrrolidone becomes amorphous carbon, Fe, upon carbonization2+The carbon is reduced into simple substance iron, the iron simple substance is used as a catalyst for graphitizing the amorphous carbon in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the part with the metal simple substance iron. Because of polyvinylpyrrolidone and soluble FeSO4·7H2O is dissolved in water, and then carbon nano tubes are added to be uniformly dispersed, so that FeSO4 Fe in (1)2+Ordered and uniform distribution is formed in the polyvinylpyrrolidone, and then the polyvinylpyrrolidone is ordered and uniformly distributed after being carbonized into amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniformly distributed.
Dispersing the carbon spheres in 2M HNO3And refluxing and heating at 120 ℃ for 12h for acid washing, filtering, washing carbon spheres with deionized water to be neutral, and then drying in vacuum for 24 h. In the process, as the metallic iron simple substance is corroded in the pickling process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) putting 8g of the carbon spheres and 2g of the lithium metal into a reaction kettle under the protection of argon, heating to 200 ℃, and preserving heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
Using the same battery system and test method as in example 1, charge and discharge cycles were performed 100 times, and the battery capacity retention rate was 86.4%.
Example 6:
30g of polyvinylpyrrolidone and 10g of CoCl2·6H2O is dissolved in 1000ml of deionized water and is stirred by magnetic force until the O is completely dissolved, thus obtaining a red solution. 70g of carbon nanotubes were added and mechanically stirred at 500rpm for 12 hours, during which time they were dispersed for 6 hours using an ultrasonic disperser to obtain a uniformly dispersed black slurry. Spray drying the black slurry, setting the temperature of an air inlet to be 200 ℃, and setting the air inlet pressure0.4MPa, and the feeding rate is 6ml/min, thus obtaining precursor powder.
And (3) putting the precursor powder into a tubular furnace, introducing nitrogen atmosphere, heating to 800 ℃, and preserving heat for 2h to obtain the partially graphitized carbon spheres with the nano-micro structure. During this carbonization process, polyvinylpyrrolidone becomes amorphous carbon, Co, when carbonized2+The carbon is reduced into simple substance cobalt, the simple substance cobalt is used as a catalyst for carbon graphitization in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the position with the metal simple substance cobalt. Due to polyvinylpyrrolidone and soluble CoCl2·6H2O is dissolved in water, and then carbon nano tubes are added to be uniformly dispersed, so that CoCl2Of (5) Co2+Ordered and uniform distribution is formed in the polyvinylpyrrolidone, and then the polyvinylpyrrolidone is ordered and uniformly distributed after being carbonized into the amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniform, and the graphitized parts are relatively ordered and uniform.
Dispersing the carbon spheres in 2M HNO3And refluxing and heating at 120 ℃ for 12h for acid washing, filtering, washing carbon spheres with deionized water to be neutral, and then drying in vacuum for 24 h. In the process, as the metallic cobalt simple substance is corroded in the acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) putting 8g of the carbon spheres and 2g of the lithium metal into a reaction kettle protected by argon, setting the temperature to be 200 ℃, and preserving the heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
The same battery system and test method as in example 1 were used, and charge and discharge cycles were performed 100 times, and the battery capacity retention ratio was 90.3%.
Example 7:
50g of polyvinylpyrrolidone and 30g of NiSO4·6H2O is dissolved in 1000ml of deionized water, and the mixture is magnetically stirred until the O is completely dissolved, so that a green solution is obtained. 50g of carbon nanotubes were added and mechanically stirred at 500rpm for 12 hours, during which time they were dispersed for 6 hours using an ultrasonic disperser to obtain a uniformly dispersed black slurry. And (3) carrying out spray drying on the black slurry, setting the temperature of an air inlet to be 200 ℃, the air inlet pressure to be 0.4MPa and the feeding rate to be 6ml/min, and obtaining precursor powder.
And (3) putting the precursor powder into a tube furnace, introducing nitrogen atmosphere, heating to 800 ℃, and preserving heat for 2h to obtain the partially graphitized carbon spheres with the nano-micro structure. During this carbonization process, polyvinylpyrrolidone becomes amorphous carbon, Ni, upon carbonization2+The carbon is reduced into simple substance nickel, the nickel simple substance is used as a catalyst for carbon graphitization in the further continuous carbonization process, so that the carbonized amorphous carbon is graphitized at the position with the metal simple substance nickel. Because of polyvinylpyrrolidone and soluble NiSO4·6H2O is dissolved in water, and then carbon nano tubes are added to be uniformly dispersed, so that NiSO4Ni in (1)2+Ordered and uniform distribution is formed in the polyvinylpyrrolidone, and then the polyvinylpyrrolidone is ordered and uniformly distributed after being carbonized into amorphous carbon, so that the graphitized parts of the amorphous carbon are relatively ordered and uniformly distributed.
Dispersing the carbon spheres in 2M HNO3And refluxing and heating at 120 ℃ for 12h for acid washing, then filtering, washing carbon spheres with deionized water to be neutral, and then drying in vacuum for 24 h. In the process, as the metallic nickel simple substance is corroded in the acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, so that the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is increased, and the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
And (3) putting 8g of the carbon spheres and 2g of the lithium metal into a reaction kettle protected by argon, setting the temperature to be 200 ℃, and preserving the heat for 20 min. The obtained material is the metal lithium-carbon composite cathode material.
Using the same battery system and test method as in example 1, charge and discharge cycles were performed 100 times, and the battery capacity retention rate was 93.7%.
In the invention, the soluble salt of the transition metal is uniformly added into the nano carbon material to form a precursor, the transition metal salt is reduced into a transition metal simple substance by carbon during carbonization treatment of the precursor, and the transition metal simple substance is used as a catalyst for graphitizing amorphous carbon when further continuing carbonization, so that the nano carbon material is graphitized at the position with the transition metal. Due to the ordered and uniform distribution of the soluble transition metal salt in the nano-carbon material, the distribution of the graphitized parts is relatively ordered and uniform.
Because the transition metal simple substance is corroded in the subsequent acid washing process, a uniform and rich pore structure is further formed on the carbon composite material, and the carbon composite material has a higher specific surface area; meanwhile, an oxygen-based functional group is introduced to the surface of the carbon composite material in the acid washing process, so that the wettability between the carbon composite material and molten metal lithium is improved. So that the molten metal lithium can be uniformly absorbed by the porous carbon-based composite material.
The carbon spherical or sphere-like carrier of the metal lithium-carbon composite material is formed by aggregating nano-base materials, and the nano-base carbon material is locally graphitized, has good conductivity, rich pore structure and higher specific surface area. In the charging and discharging process of the battery, the graphitized part guides the deposition of the metal lithium, so that the deposited lithium is more uniform, the generation of lithium dendrites is reduced, the cycle life of a metal lithium cathode is prolonged, and meanwhile, the utilization rate of the metal lithium is improved by virtue of the abundant pore structure and the three-dimensional conductive network, so that the energy density of the battery is improved.
The metal lithium-carbon composite material prepared by the method can also be suitable for liquid or solid or gel battery systems and the like. Of course, the lithium metal can be replaced by other lithium metal to be applied to battery systems similar to the system, such as: potassium batteries, sodium batteries, and the like. The method has simple process, and is suitable for large-scale production. The liquid and solid batteries prepared by the invention have the characteristics of high energy density and long cycle life.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features of the present invention described in the embodiments may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.

Claims (8)

1. A preparation method of a metal lithium-carbon composite material comprises the following steps:
the method comprises the following steps: dissolving a nano conductive carbon material, a high molecular surfactant and a soluble transition metal salt in water, and then carrying out spray drying to obtain a precursor;
step two: carbonizing the precursor to obtain carbon spheres;
step three: washing the carbon spheres with water to neutrality after acid washing;
step four: co-melting the carbon spheres washed to be neutral by water after acid washing and the metal lithium in an argon atmosphere to obtain a metal lithium-carbon composite material; the metal lithium-carbon composite material comprises a spherical or sphere-like carrier of carbon and metal lithium formed in pores of the spherical or sphere-like carrier of the carbon, wherein the spherical or sphere-like carrier of the carbon is formed by agglomeration of nano-based carbon materials, and the nano-based carbon materials are partially graphitized.
2. The method of claim 1, wherein the carbonization is performed by heating to 500-1000 ℃ in a nitrogen atmosphere and maintaining the temperature for 1-12 h.
3. The method of preparing a metallic lithium-carbon composite material according to claim 1, wherein the carbonization treatment is heating to 800 ℃ in a nitrogen atmosphere and holding for 6 hours.
4. The method of preparing a metallic lithium-carbon composite material according to claim 1, wherein the nano conductive carbon material is a carbon nanotube, a carbon nanofiber, graphene, or ketjen black.
5. The method of preparing a metallic lithium-carbon composite material according to claim 1 or 4, wherein the polymeric surfactant is polyvinylpyrrolidone, cationic starch, carboxymethyl cellulose, or hydroxypropyl cellulose.
6. The method of preparing a metallic lithium-carbon composite material according to claim 1 or 4, wherein the soluble transition metal salt is an iron salt, a cobalt salt or a nickel salt.
7. The method of preparing a metallic lithium-carbon composite material according to claim 6, wherein the iron salt is ferric nitrate or ferrous sulfate; the cobalt salt is cobalt chloride or cobalt sulfate; the nickel salt is nickel nitrate, nickel sulfate or nickel acetate.
8. The method of claim 1, wherein the spray-dried inlet temperature is 105 ℃ to 300 ℃, the inlet pressure is 0.2MPa to 0.6MPa, and the feed rate is 3ml/min to 15 ml/min.
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