CN110970665A - SnS2Preparation method of/HNTs composite lithium ion battery - Google Patents
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a SnS2The preparation method of the/HNTs composite lithium ion battery comprises the following steps: 0.4g of SnS is weighed2Mixing the/HNTs composite negative electrode material with 0.05g of polyvinylidene fluoride, dripping N-methyl pyrrolidone, stirring and mixing uniformly to form slurry, uniformly coating the slurry on a copper foil, carrying out vacuum drying, punching into a circular negative electrode piece with the diameter of 14mm, carrying out vacuum drying, assembling into a battery in a glove box filled with argon, wherein the battery takes a lithium piece as a counter electrode, a Celgard2400 polypropylene diaphragm is used as the diaphragm, 1mol/l LiPF6 of electrolyte is blended into ethylene carbonate EC/dimethyl carbonate DMC/diethyl carbonate EMC solution, and dripping the electrolyte until the diaphragm, the positive electrode and the negative electrode are just fully soaked.
Description
Technical Field
The invention relates to a preparation method of a battery material, and particularly relates to SnS2A preparation method of/HNTs composite lithium ion battery.
Background
The lithium ion battery has been developed as an energy storage system in the last sixty-seven decades, and makes a remarkable contribution to the development of technologies such as electronic equipment, aerospace, wireless remote control and the like. However, with the rapid development of the world economy, people put higher demands on the capacity and the cycle performance of the lithium ion battery. Currently, research on lithium ion battery negative electrode materials is very intensive. In recent years, transition metal sulfides have become one of the ideal negative electrode materials for lithium ion batteries, in which Co is present9S8Having a high theoretical specific volumeThe lithium ion battery has the advantages of high capacity (539mA · h/g), abundant reserves, low price, environmental friendliness, good conductivity, small electrode polarization, and small volume change in the circulation process compared with an alloy mechanism material, and in addition, the high voltage platform ensures the good safety performance of the lithium ion battery. However, the extreme volume expansion during lithium intercalation causes pulverization of the electrode material, resulting in peeling of the electrode material from the electrode, and a large irreversible capacity loss even at the time of charge and discharge at a small current density. In addition, their low first coulombic efficiency, high rate charge-discharge capacity, and poor cycle stability are due to their sluggish ion transport kinetics, which all limit their application in lithium ion batteries. How to improve Co9S8The active material serving as the negative electrode of the lithium ion battery has high utilization rate, long cycle life and improved rate performance. The invention takes cobalt nitrate hexahydrate, molybdenum acetylacetonate, stannic chloride pentahydrate and the like as main raw materials, and introduces a biomass composite carbon material to prepare a novel lithium ion battery cathode material, which can effectively improve the electrochemical performance of the lithium ion battery.
Disclosure of Invention
The invention discloses a SnS2A preparation method of a/HNTs composite lithium ion battery mainly solves the problems of low specific capacity, poor cycle performance and the like of the traditional lithium ion battery in the current market.
SnS2The preparation method of the/HNTs composite lithium ion battery is characterized by comprising the following steps:
0.4g of SnS is weighed2Mixing the/HNTs composite negative electrode material with 0.05g of polyvinylidene fluoride, dripping 2ml of N-methyl pyrrolidone, stirring and mixing uniformly to form slurry, uniformly coating the slurry on a copper foil, drying at 120 ℃ in vacuum for 10min, punching into a circular negative electrode piece with the diameter of 14mm, drying at 85 ℃ in vacuum for 24h, assembling into a 2016 type battery in a glove box filled with argon, wherein the battery takes a lithium piece as a counter electrode, a Celgard2400 polypropylene diaphragm is used as the diaphragm, 1mol/l LiPF6 of electrolyte is dissolved into a vinyl carbonate EC/dimethyl carbonate/diethyl carbonate EMC solution, and dripping the electrolyte until the diaphragm, the positive electrode and the negative electrode are just and fully soaked.
SnS2The preparation method of the/HNTs composite negative electrode material comprises the following steps:
1) weighing 2-34 parts by weight of halloysite nanotube and 9 parts by weight of Co (NO)3)2·6H2O and 10 parts by weight of C10H16MoO6Dissolving the mixture in a mixed solvent of 150 parts by weight of glycerol and isopropanol, adding 20-60 parts by weight of biomass composite carbon material, magnetically stirring for 30min, transferring the mixture into a reaction kettle, reacting for 12h at 180 ℃, filtering, washing the precipitate obtained after the reaction for 3-4 times by using 200 parts by weight of absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain mixed powder;
2) weighing 10 parts by weight of the mixed powder, putting the mixed powder into a reaction kettle, adding 40 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran and 2 parts by weight of citric acid, magnetically stirring for 30min, ultrasonically dispersing for 1H, slowly adding 9 parts by weight of stannic dichloride pentahydrate and 20 parts by weight of sodium thiosulfate pentahydrate, heating to 160 ℃, reacting for 24H, cooling at normal temperature, washing for 3 times by using 180 parts by weight of pure water and 180 parts by weight of absolute ethyl alcohol respectively, drying for 12H in a 60 ℃ vacuum drying box, mixing the obtained dried powder with 50 parts by weight of sulfur powder, introducing 10% H2Carrying out vulcanization treatment on 90% of Ar mixed gas at 700 ℃ for 5h, and naturally cooling to room temperature to obtain SnS2the/HNTs composite anode material.
The preparation method of the biomass composite carbon material in the step 1) is characterized in that:
weighing 100 parts by weight of corncobs, placing the corncobs in a 105 ℃ drying oven for drying for 24 hours, crushing the corncobs by a crusher, sieving the corncobs by a 20-mesh sieve, taking 40 parts by weight of sieved corncob powder in a reaction kettle, adding 80 parts by weight of concentrated phosphoric acid with the mass concentration of 85% and 60 parts by weight of deionized water, magnetically stirring for 30 minutes, placing the corncob powder in a 230 ℃ high-temperature drying oven for heat preservation for 12 hours, taking out the product for suction filtration, placing the suction filtration product in the 105 ℃ drying oven for drying, fully mixing the product with 28 parts by weight of PbO powder, placing the product in a crucible, placing the crucible in a high-temperature tubular furnace with the nitrogen flow rate of 1.0L/min for activation, heating to 480 ℃ at the speed of 5 ℃/min, preserving the temperature for activation for 30 minutes, taking out for natural cooling, washing and activating the obtained sample by 100 parts by weight of 0.3% diluted HCl solution for.
Has the advantages that:
1. the agricultural waste corncob is used as a material, and is carbonized and activated to obtain the bulky and porous biomass activated carbon, so that the cost is low, the environment is very friendly, the problem of environmental pollution can be solved, and the energy crisis can be relieved.
2. The biomass activated carbon material is introduced with phosphorus, so that the theoretical capacity of the lithium ion battery is improved, and the conductivity and the battery capacity of the biomass activated carbon are further improved under the synergistic effect of cobalt, molybdenum and other transition metal sulfides.
3. The biological activated carbon is loose and porous, the porous carbon nanotube is also a porous material, and the SnS prepared by compounding the biological activated carbon and the porous carbon nanotube2the/HNTs composite negative electrode material contains a large number of microporous structures and specific surface areas, and can effectively promote the circulation of electrolyte in a battery when being used as a negative electrode material of a lithium battery, form a good conductive network, improve the electrochemical reaction rate and improve the electrochemical performance of the battery.
Detailed Description
Example 1
SnS2The preparation method of the/HNTs composite lithium ion battery is characterized by comprising the following steps:
0.4g of SnS is weighed2Mixing the/HNTs composite negative electrode material with 0.05g of polyvinylidene fluoride, dripping 2ml of N-methyl pyrrolidone, stirring and mixing uniformly to form slurry, uniformly coating the slurry on a copper foil, drying at 120 ℃ in vacuum for 10min, punching into a circular negative electrode piece with the diameter of 14mm, drying at 85 ℃ in vacuum for 24h, assembling into a 2016 type battery in a glove box filled with argon, wherein the battery takes a lithium piece as a counter electrode, a Celgard2400 polypropylene diaphragm is used as the diaphragm, 1mol/l LiPF6 of electrolyte is dissolved into a vinyl carbonate EC/dimethyl carbonate/diethyl carbonate EMC solution, and dripping the electrolyte until the diaphragm, the positive electrode and the negative electrode are just and fully soaked.
SnS2The preparation method of the/HNTs composite negative electrode material comprises the following steps:
1) weighing 10 parts by weight of halloysite nanotube and 9 parts by weight of Co (NO)3)2·6H2O and 10 parts by weight of C10H16MoO6Dissolving the mixture in 150 parts by weight of a mixed solvent of glycerol and isopropanol, adding 50 parts by weight of a biomass composite carbon material, magnetically stirring for 30min, transferring the mixture into a reaction kettle, reacting for 12h at 180 ℃, filtering, washing the precipitate obtained after the reaction for 3-4 times by using 200 parts by weight of absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain mixed powder;
2) weighing 10 parts by weight of the mixed powder, putting the mixed powder into a reaction kettle, adding 40 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran and 2 parts by weight of citric acid, magnetically stirring for 30min, ultrasonically dispersing for 1H, slowly adding 9 parts by weight of stannic dichloride pentahydrate and 20 parts by weight of sodium thiosulfate pentahydrate, heating to 160 ℃, reacting for 24H, cooling at normal temperature, washing for 3 times by using 180 parts by weight of pure water and 180 parts by weight of absolute ethyl alcohol respectively, drying for 12H in a 60 ℃ vacuum drying box, mixing the obtained dried powder with 50 parts by weight of sulfur powder, introducing 10% H2Carrying out vulcanization treatment on 90% of Ar mixed gas at 700 ℃ for 5h, and naturally cooling to room temperature to obtain SnS2the/HNTs composite anode material.
The preparation method of the biomass composite carbon material comprises the following steps:
weighing 100 parts by weight of corncobs, placing the corncobs in a 105 ℃ drying oven for drying for 24 hours, crushing the corncobs by a crusher, sieving the corncobs by a 20-mesh sieve, taking 40 parts by weight of sieved corncob powder in a reaction kettle, adding 80 parts by weight of concentrated phosphoric acid with the mass concentration of 85% and 60 parts by weight of deionized water, magnetically stirring for 30 minutes, placing the corncob powder in a 230 ℃ high-temperature drying oven for heat preservation for 12 hours, taking out the product for suction filtration, placing the suction filtration product in the 105 ℃ drying oven for drying, fully mixing the product with 28 parts by weight of PbO powder, placing the product in a crucible, placing the crucible in a high-temperature tubular furnace with the nitrogen flow rate of 1.0L/min for activation, heating to 480 ℃ at the speed of 5 ℃/min, preserving the temperature for activation for 30 minutes, taking out for natural cooling, washing and activating the obtained sample by 100 parts by weight of 0.3% diluted HCl solution for.
Example 2
Exactly the same as example 1, except that: adding 2 parts by weight of halloysite nanotubes and 60 parts by weight of biomass composite carbon material.
Example 3
Exactly the same as example 1, except that: 6 parts by weight of halloysite nanotubes and 55 parts by weight of biomass composite carbon material are added.
Example 4
Exactly the same as example 1, except that: adding 14 parts by weight of halloysite nanotubes and 45 parts by weight of biomass composite carbon material.
Example 5
Exactly the same as example 1, except that: adding 18 parts by weight of halloysite nanotubes and 40 parts by weight of biomass composite carbon material.
Example 6
Exactly the same as example 1, except that: adding 22 parts by weight of halloysite nanotubes and 35 parts by weight of biomass composite carbon material.
Example 7
Exactly the same as example 1, except that: adding 26 parts by weight of halloysite nanotubes and 30 parts by weight of biomass composite carbon material.
Example 8
Exactly the same as example 1, except that: adding 30 parts by weight of halloysite nanotubes and 25 parts by weight of biomass composite carbon material.
Example 9
Exactly the same as example 1, except that: adding 34 parts by weight of halloysite nanotubes and 20 parts by weight of biomass composite carbon material.
Example 10
1) Weighing 10 parts by weight of halloysite nanotube and 9 parts by weight of Co (NO)3)2·6H2O and 10 parts by weight of C10H16MoO6Dissolving the mixture in 150 parts by weight of mixed solvent of glycerol and isopropanol, adding 50 parts by weight of biomass composite carbon material, magnetically stirring for 30min, transferring the mixture to a reaction kettle, reacting for 12h at 180 ℃, filtering, washing the precipitate obtained after the reaction for 3-4 times by using 200 parts by weight of absolute ethyl alcohol, drying for 12h at 60 ℃, soaking for 1h by using 100 parts by weight of 2% acetic acid solution, and drying for 5h at 85 ℃ to obtain the productMixing the powder;
2) weighing 10 parts by weight of the mixed powder, putting the mixed powder into a reaction kettle, adding 40 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran and 2 parts by weight of citric acid, magnetically stirring for 30min, ultrasonically dispersing for 1H, slowly adding 9 parts by weight of stannic dichloride pentahydrate and 20 parts by weight of sodium thiosulfate pentahydrate, heating to 160 ℃, reacting for 24H, cooling at normal temperature, washing for 3 times by using 180 parts by weight of pure water and 180 parts by weight of absolute ethyl alcohol respectively, drying for 12H in a 60 ℃ vacuum drying box, mixing the obtained dried powder with 50 parts by weight of sulfur powder, introducing 10% H2Carrying out vulcanization treatment on 90% of Ar mixed gas at 700 ℃ for 5h, and naturally cooling to room temperature to obtain SnS2the/HNTs composite anode material.
The preparation method of the biomass composite carbon material comprises the following steps:
weighing 100 parts by weight of corncobs, placing the corncobs in a 105 ℃ drying oven for drying for 24 hours, crushing the corncobs by a crusher, sieving the corncobs by a 20-mesh sieve, taking 40 parts by weight of sieved corncob powder in a reaction kettle, adding 80 parts by weight of concentrated phosphoric acid with the mass concentration of 85% and 60 parts by weight of deionized water, magnetically stirring for 30 minutes, placing the corncob powder in a 230 ℃ high-temperature drying oven for heat preservation for 12 hours, taking out the product for suction filtration, placing the suction filtration product in the 105 ℃ drying oven for drying, fully mixing the product with 28 parts by weight of PbO powder, placing the product in a crucible, placing the crucible in a high-temperature tubular furnace with the nitrogen flow rate of 1.0L/min for activation, heating to 480 ℃ at the speed of 5 ℃/min, preserving the temperature for activation for 30 minutes, taking out for natural cooling, washing and activating the obtained sample by 100 parts by weight of 0.3% diluted HCl solution for.
Comparative example 1
Exactly the same as example 1, except that: no biomass composite carbon material is added.
Comparative example 2
Exactly the same as example 1, except that: the sunflower disc is used for replacing corncobs in the process of preparing the biomass composite carbon material.
Comparative example 3
Exactly the same as example 1, except that: PbO powder is not added in the process of preparing the biomass composite carbon material.
Comparative example 4
Exactly the same as example 1, except that: concentrated phosphoric acid is not added in the process of preparing the biomass composite carbon material.
Comparative example 5
Exactly the same as example 1, except that: concentrated sulfuric acid is used for replacing concentrated phosphoric acid in the process of preparing the biomass composite carbon material.
Comparative example 6
Exactly the same as example 1, except that: c is not added when the lithium ion battery cathode material is prepared10H16MoO6。
Comparative example 7
Exactly the same as example 1, except that: co (NO) is not added when preparing the lithium ion battery cathode material3)2·6H2O。
Comparative example 8
Exactly the same as example 1, except that: no halloysite nanotube is added when the lithium ion battery cathode material is prepared.
Comparative example 9
Exactly the same as example 1, except that: CoSO used for preparing lithium ion battery cathode material4·7H2O replaces cobalt nitrate hexahydrate.
Comparative example 10
Exactly the same as example 10, except that: when the lithium ion battery cathode material is prepared, a product obtained by drying for 12 hours at the temperature of 60 ℃ in the step 1) is soaked in 100 parts by weight of lactic acid solution with the mass fraction of 2% for 1 hour, and is dried for 5 hours at the temperature of 85 ℃ to obtain mixed powder.
SnS prepared in examples 1 to 10 and comparative examples 1 to 10 was treated in the following manner2And carrying out performance test on the/HNTs composite lithium ion battery cathode material.
Constant current charge and discharge test of the battery is carried out on a Xinwei detection system, and Cyclic Voltammetry (CV) and alternating current impedance (EIS) tests are carried out on a CHI660E type electrochemical workstation (scanning voltage: 0.01-3V, scanning speed 0.1mV S)-1；EIS：0.05Hz~100kHz）。
Testing of battery charging and discharging performance
From examples 1-9, it can be found that the SnS prepared in example 1 is in a proportioning environment2After the negative electrode material of the/HNTs composite lithium ion battery is assembled into the battery, the test result of the charge and discharge performance is the best, the specific capacity reaches 1584mAh/g, and the SnS prepared in the embodiments 2-92The charge-discharge performance of the/HNTs composite lithium ion battery cathode material assembled battery is not particularly ideal compared with that of the embodiment 1, which shows that the SnS with high electrochemical performance can be prepared by the raw material proportion and the operation process in the embodiment 12The possible reason for the/HNTs composite lithium ion battery cathode material is that phosphorus element is introduced into a biomass activated carbon material for preparing the cathode material, so that the theoretical capacity of the lithium ion battery is favorably improved, the conductivity and the battery capacity of the biomass activated carbon are further improved under the synergistic effect of transition metal sulfides such as cobalt, molybdenum and the like, in addition, the biomass activated carbon is loose and porous, the porous carbon nanotube is also a porous material, and the SnS prepared by compounding the biomass activated carbon and the porous metal sulfide is a porous material2the/HNTs composite negative electrode material contains a large number of microporous structures and specific surface areas, and can effectively promote the circulation of electrolyte in a battery when being used as a negative electrode material of a lithium battery, form a good conductive network, improve the electrochemical reaction rate and improve the electrochemical performance of the battery. In addition, comparative examples 1-5 illustrate the addition of the biomass composite carbon material to SnS2The electrochemical performance of the/HNTs composite lithium ion battery cathode material is greatly influenced, and the comparative examples 6-9 illustrate that SnS is prepared2The selection of the raw materials and conditions of the/HNTs composite lithium ion battery negative electrode material has outstanding influence on the electrochemical performance of the battery. The applicant unexpectedly finds that after a product obtained by drying for 12 hours at 60 ℃ in the step 1) is soaked in 100 parts by weight of 2% by mass of acetic acid solution for 1 hour, although the specific capacity is reduced, the specific capacity retention rate is greatly improved, and the specific capacity retention rate of the 200 th charging and discharging electrode material can still reach 95.1%, so that the product obtained by drying for 12 hours at 60 ℃ has an unexpected promotion effect on the specific capacity retention rate of the battery.
Claims (3)
1. SnS2The preparation method of the/HNTs composite lithium ion battery is characterized by comprising the following steps:
0.4g of SnS is weighed2Mixing the/HNTs composite negative electrode material with 0.05g of polyvinylidene fluoride, dripping 2ml of N-methyl pyrrolidone, stirring and mixing uniformly to form slurry, uniformly coating the slurry on a copper foil, drying at 120 ℃ in vacuum for 10min, punching into a circular negative electrode piece with the diameter of 14mm, drying at 85 ℃ in vacuum for 24h, assembling into a 2016 type battery in a glove box filled with argon, wherein the battery takes a lithium piece as a counter electrode, a Celgard2400 polypropylene diaphragm is used as the diaphragm, 1mol/l LiPF6 of electrolyte is dissolved into a vinyl carbonate EC/dimethyl carbonate/diethyl carbonate EMC solution, and dripping the electrolyte until the diaphragm, the positive electrode and the negative electrode are just and fully soaked.
2. The SnS of claim 12The preparation method of the/HNTs composite lithium ion battery is characterized in that the SnS composite lithium ion battery is prepared by the following steps2The preparation method of the/HNTs composite negative electrode material comprises the following steps:
1) weighing 2-34 parts by weight of halloysite nanotube and 9 parts by weight of Co (NO)3)2·6H2O and 10 parts by weight of C10H16MoO6Dissolving the mixture in a mixed solvent of 150 parts by weight of glycerol and isopropanol, adding 20-60 parts by weight of biomass composite carbon material, magnetically stirring for 30min, transferring the mixture into a reaction kettle, reacting for 12h at 180 ℃, filtering, washing the precipitate obtained after the reaction for 3-4 times by using 200 parts by weight of absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain mixed powder;
2) weighing 10 parts by weight of the mixed powder, putting the mixed powder into a reaction kettle, adding 40 parts by weight of deionized water, 20 parts by weight of tetrahydrofuran and 2 parts by weight of citric acid, magnetically stirring for 30min, ultrasonically dispersing for 1H, slowly adding 9 parts by weight of stannic dichloride pentahydrate and 20 parts by weight of sodium thiosulfate pentahydrate, heating to 160 ℃, reacting for 24H, cooling at normal temperature, washing for 3 times by using 180 parts by weight of pure water and 180 parts by weight of absolute ethyl alcohol respectively, drying for 12H in a 60 ℃ vacuum drying box, mixing the obtained dried powder with 50 parts by weight of sulfur powder, introducing 10% H2+90% of Ar mixed gas, entering at 700 DEG CCarrying out vulcanization treatment for 5h, naturally cooling to room temperature to obtain SnS2the/HNTs composite anode material.
3. The SnS of claim 22The preparation method of the/HNTs composite lithium ion battery is characterized in that in the step 1), the preparation method of the biomass composite carbon material in the step 1) is as follows:
weighing 100 parts by weight of corncobs, placing the corncobs in a 105 ℃ drying oven for drying for 24 hours, crushing the corncobs by a crusher, sieving the corncobs by a 20-mesh sieve, taking 40 parts by weight of sieved corncob powder in a reaction kettle, adding 80 parts by weight of concentrated phosphoric acid with the mass concentration of 85% and 60 parts by weight of deionized water, magnetically stirring for 30 minutes, placing the corncob powder in a 230 ℃ high-temperature drying oven for heat preservation for 12 hours, taking out the product for suction filtration, placing the suction filtration product in the 105 ℃ drying oven for drying, fully mixing the product with 28 parts by weight of PbO powder, placing the product in a crucible, placing the crucible in a high-temperature tubular furnace with the nitrogen flow rate of 1.0L/min for activation, heating to 480 ℃ at the speed of 5 ℃/min, preserving the temperature for activation for 30 minutes, taking out for natural cooling, washing and activating the obtained sample by 100 parts by weight of 0.3% diluted HCl solution for.
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