CN117497723A - Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery - Google Patents
Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 71
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 15
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- 238000001914 filtration Methods 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 13
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
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- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
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- 238000003763 carbonization Methods 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of lithium ion battery preparation materials, in particular to a preparation method of a composite anode material of which MOF derived carbon coated silicon nano particles of a lithium ion battery are limited to MXene, which comprises the following steps: step 1, dispersing nano silicon and polyvinylpyrrolidone in a solvent, stirring and mixing for 12 hours, and filtering, washing and drying to obtain PVP@Si precursor; step 2, dispersing PVP@Si and 2-methylimidazole in the step 1 in a solvent, and stirring and mixing for 1h to obtain a mixed solution; step 3, dispersing cobalt nitrate hexahydrate in the solution, and carrying out ultrasonic treatment for 0.5h to obtain the solution; step 4, mixing and stirring the mixed solution in the step 2 and the cobalt nitrate solution in the step 3; the composite material of Co-Si@MXene, co-Si/C@MXene and Si/C@MXene obtained by the method can be used as a lithium ion battery cathode material, so that the cycle stability and the cycle life of the battery are improved. When the material is used as a negative electrode material of a lithium ion battery, the volume expansion can be slowed down, the lithium ion transmission path can be shortened, and the conductivity of the material can be improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery preparation materials, in particular to a preparation method of a composite anode material with MOF derived carbon coated silicon nanoparticles limited to MXene.
Background
Lithium Ion Batteries (LIBs) have enjoyed tremendous success in a variety of energy storage devices due to their high energy density, long cycle life, and environmental benefits, but the dramatic increase in energy demand has prompted the search for next generation LIBs with higher energy densities. In order to realize a lithium ion battery with high specific capacity, the negative electrode material of the graphite negative type is also widely applied, and has great advantages in the aspects of wide sources, good economy and the like. Because the current commercial graphite carbon anode material has low theoretical capacity (372 mAh g) -1 ) The demand for lithium ions with high specific capacity cannot be satisfied. Various advanced anode materials have been developed. Of these candidate materials, silicon has the most potential because of its ultra-high theoretical specific capacity (≡4200mAh g) -1 ) The lithium ion battery anode material has rich reserve, low working voltage and low price, and is a very potential lithium ion battery anode material. However, during lithiation/delithiation, the silicon volume changes greatly, the Solid Electrolyte Interface (SEI) layer is unstable, the conductivity is low, resulting in rapid capacity fading, large irreversible capacity, and poor rate performance.
Several strategies have been proposed to solve these problems. From a material perspective, the main approach is to reduce the silicon particle size to the nanometer scale, creating a porous structure. MXenes are a class of two-dimensional transition metal carbides and nitrides that are considered to be a promising energy storage material due to their metallic conductivity, good hydrophilicity, and good mechanical properties. MXene can bind various nanomaterials (e.g., carbon nanotubes, polymers, and graphiteAlkene, as a conductive substrate, is used to fabricate independent composite membranes by vacuum filtration for applications in energy storage devices such as lithium ion batteries, supercapacitors, and lithium sulfur batteries. In this respect, several independent electrodes have been reported to be based on 2D Ti 3 C 2 T x The MXene or graphene conductive adhesive comprises a super-capacitor carbon electrode and a carbon electrode, so that the volume change of silicon nano particles and silicon is limited, and good circulation stability is ensured. In addition, the MXene framework provides high conductivity, coating the silicon nanoparticles, increasing charge transport and thus improving the rate performance of the electrode. The silicon nanoparticles in turn prevent the aggregation of the MXene nanoplatelets and expand their interlayer distance. Therefore, the MXene coated nano silicon particles have good flexibility, excellent stability, high capacity and excellent rate performance, and show that the MXene coated nano silicon particles have potential of being used as a negative electrode material of a lithium ion battery.
Therefore, the preparation method of the lithium ion battery anode material has the advantages of simple process, good cycle performance and multiplying power charge and discharge performance, high and stable charge and discharge efficiency for constant current, lower impedance and capability of improving the transmission speed of lithium ions, and is a technical problem in the field compared with the preparation method of the lithium ion battery anode material capable of reducing the cost in the preparation process.
Disclosure of Invention
The invention aims to solve the problems, and provides a preparation method of a composite anode material of MXene limited by MOF derived carbon coated silicon nano particles of a lithium ion battery, which can overcome the defect that the capacity of a battery using a silicon anode material in the prior art is excessively fast in decay, and mainly realizes the circulation of high specific capacity.
The invention realizes the aim through the following technical scheme, and the preparation method of the MOF derived carbon coated silicon nanoparticle of the lithium ion battery is limited to an MXene composite anode material, and comprises the following steps:
step 1, dispersing nano silicon and polyvinylpyrrolidone in a solvent, stirring and mixing for 12 hours, and filtering, washing and drying to obtain PVP@Si precursor;
step 2, dispersing PVP@Si and 2-methylimidazole in the step 1 in a solvent, and stirring and mixing for 1h to obtain a mixed solution;
step 3, dispersing cobalt nitrate hexahydrate in the solution, and carrying out ultrasonic treatment for 0.5h to obtain the solution;
step 4, mixing and stirring the mixed solution in the step 2 and the cobalt nitrate solution in the step 3 to obtain a MOF silicon-coated material;
wherein the ratio of the amounts of the substances of 2-methylimidazole and cobalt nitrate hexahydrate is: 2-5;
step 5, mixing the mixed solution obtained in the step 4 with the MXene solution, stirring and mixing the mixture for 24, and filtering, washing and drying the mixture to obtain the Co/Si@MXene composite anode material;
step 6, burning the Co/Si@MXene composite anode material in the step 5 in a tubular furnace for 3 hours to obtain a Co-Si/C@MXene composite anode material;
and 7, carrying out sulfuric acid washing on the Co-Si/C@MXene composite anode material in the step 6 to obtain the Si/C@MXene composite anode material.
Preferably, the ratio of the amounts of the substances of 2-methylimidazole in step 2 and cobalt nitrate hexahydrate in step 3 is: 2-5.
Preferably, the particle size of the nano silicon in the step 1 is 60-100nm.
Preferably, the dispersing solvent in the step 1 is absolute ethanol.
Preferably, the dispersing solvent in the step 2 is anhydrous methanol.
Preferably, in the sintering in the tube furnace in the step 6, the temperature is raised to 800 ℃ at a heating rate of 3 ℃/min in an inert gas argon or nitrogen environment, and then the sintering is performed for 3 hours.
Preferably, in the step 7, when the Co-Si/C@MXene composite anode material is pickled by sulfuric acid, 2mol/L dilute sulfuric acid is used for soaking for 12 hours, and then the Si/C@MXene composite anode material is obtained through filtering, washing and drying.
Preferably, the washing solvents are all anhydrous methanol.
The beneficial effects of the invention are as follows:
1. the composite material of Co-Si@MXene, co-Si/C@MXene and Si/C@MXene obtained by the method can be used as a lithium ion battery cathode material, so that the cycle stability and the cycle life of the battery are improved. When the material is used as a negative electrode material of a lithium ion battery, the volume expansion can be slowed down, the lithium ion transmission path can be shortened, and the conductivity of the material can be improved. The prepared lithium ion battery has the advantages of high stability, long cycle life, good multiplying power performance and the like, and can effectively meet the practical application requirements of the lithium ion battery with high energy density.
2. The porous Co-Si@MXene, co-Si/C@MXene and Si/C@MXene composite material prepared by the method has the advantages of more than micron-sized size, high purity and high tap density.
3. All the template MOFs of the invention can be directly sintered and removed without acid-base treatment, and the preparation process is simple, the raw materials are cheap and easy to obtain, the cost is low, and the environment is friendly.
Drawings
FIG. 1 is an SEM image of a Co-Si@MXene composite anode material prepared by the method;
FIG. 2 is a charge-discharge curve of the Co-Si@MXene composite anode material prepared by the invention;
FIG. 3 is a specific capacity cycle chart of the Co-Si@MXene composite anode material prepared by the invention;
FIG. 4 is a magnification view of the Co-Si@MXene composite anode material prepared by the invention;
FIG. 5 is an SEM image of the Co-Si/C@MXene composite anode material prepared by the invention;
FIG. 6 is a charge-discharge curve of the Co-Si/C@MXene composite anode material prepared by the invention;
FIG. 7 is a specific capacity cycle chart of the Co-Si/C@MXene composite anode material prepared by the invention;
FIG. 8 is a magnification view of a Co-Si/C@MXene composite anode material prepared by the invention;
FIG. 9 is an SEM image of the Si/C@MXene composite anode material prepared by the invention;
FIG. 10 is a charge-discharge curve of the Si/C@MXene composite anode material prepared by the invention;
FIG. 11 is a specific capacity cycle chart of the Si/C@MXene composite anode material prepared by the invention;
FIG. 12 is a magnification view of a Si/C@MXene composite anode material prepared by the invention;
FIG. 13 is a ZIF-67SEM image;
FIG. 14 is an SEM image of MXene.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the MOF-derived carbon-coated silicon nanoparticle of the lithium ion battery is limited to an MXene composite anode material, and comprises the following steps of:
step 1, dissolving 0.2g of silicon and 1.0g of polyvinylpyrrolidone in 60ml of ethanol solution, stirring at room temperature for 12 hours, and then filtering, washing and drying to obtain PVP@Si material;
step 2, dispersing PVP@Si and 1.642g of 2-methylimidazole in the step 1 into 100ml of anhydrous methanol solution, and stirring and mixing for 1h to obtain a mixed solution;
step 3, dispersing 1.456g of cobalt nitrate hexahydrate in 100ml of anhydrous methanol solution, and carrying out ultrasonic treatment for 0.5h to obtain a solution;
step 4, mixing and stirring the mixed solution in the step 2 and the cobalt nitrate solution in the step 3 to obtain a MOF silicon-coated material;
wherein the ratio of the amounts of the substances of 2-methylimidazole and cobalt nitrate hexahydrate is: 2:5;
step 5, mixing the mixed solution in the step 4 with 50ml (2 mol/ml) of MXene solution, stirring and mixing for 24, and filtering, washing and drying to obtain a Co/Si@MXene composite anode material;
step 6, when the Co/Si@MXene composite anode material in the step 5 is sintered in a tubular furnace, heating to 800 ℃ at a heating rate of 3 ℃/min in an inert gas argon or nitrogen environment, and calcining for 3 hours to obtain the Co-Si/C@MXene composite anode material;
and 7, soaking the Co-Si/C@MXene composite anode material in the step 6 in 2mol/L sulfuric acid for 12 hours, and filtering, washing and drying to obtain the Si/C@MXene composite anode material.
Example 2
The preparation method of the MOF-derived carbon-coated silicon nanoparticle of the lithium ion battery is limited to an MXene composite anode material, and comprises the following steps of:
step 1, dissolving 0.14g of silicon, 0.7g of polyvinylpyrrolidone and 1.54g of 2-methylimidazole in 50ml of ethanol solution, stirring at room temperature for 12 hours, and then filtering, washing and drying to obtain PVP@Si material;
step 2, dissolving 1.455g of cobalt nitrate hexahydrate in 50ml of absolute methanol solution, pouring 50ml (2 mol/ml) of MXene solution after dissolving, and stirring at room temperature for 1h;
step 3, dissolving PVP@Si in the step 1 in 50ml of absolute methanol, slowly pouring the mixed solution in the step 2 into the step 1, stirring for 24 hours at room temperature, and centrifuging, washing and freeze-drying to obtain a Co/Si@MXene composite anode material;
wherein the ratio of the amounts of the substances of 2-methylimidazole and cobalt nitrate hexahydrate is: 2:5;
step 4, when the Co/Si@MXene composite anode material in the step 3 is sintered in a tubular furnace, heating to 700 ℃ at a heating rate of 1 ℃/min in an inert gas argon or nitrogen environment, and calcining for 3 hours to obtain the Co-Si/C@MXene composite anode material;
and 5, soaking the Co-Si/C@MXene composite anode material in the step 4 in 2mol/L hydrochloric acid for 12 hours, and filtering, washing and drying to obtain the Si/C@MXene composite anode material.
Example 3
The preparation method of the MOF-derived carbon-coated silicon nanoparticle of the lithium ion battery is limited to an MXene composite anode material, and comprises the following steps of:
step 1, adding 0.03g of silicon, 0.15g of polyvinylpyrrolidone and 10ml of absolute methanol into a ball milling tank, and ball milling for 2 hours at a rotating speed of 500 rpm;
step 2, after ball milling in the step 1 is completed, adding 1.54g of 2-methylimidazole and 5ml of absolute methanol into a ball milling tank in the step 1, ball milling for 1h at a rotating speed of 500rmp, centrifuging, washing, drying, and collecting mixed powder;
step 3, 1.455g of cobalt nitrate hexahydrate is dissolved in 10ml of absolute methanol solution, 10ml (2 mmol/ml) of MXene solution and cobalt nitrate solution are measured and mixed, and stirring treatment is carried out for 0.5h at room temperature;
step 4, adding the mixed powder in the step 2 and the mixed solution in the step 3 into a ball milling tank, ball milling for 4 hours at a rotating speed of 500rmp, transferring the mixed powder into an autoclave, heating to 200 ℃, preserving heat for 12 hours, and then filtering, washing and drying to obtain a Co/Si@MXene composite anode material;
wherein the ratio of the amounts of the substances of 2-methylimidazole and cobalt nitrate hexahydrate is: 2:5;
step 5, when the Co/Si@MXene composite anode material in the step 4 is sintered in a tubular furnace, heating to 700 ℃ at a heating rate of 1 ℃/min in an inert gas argon or nitrogen environment, and calcining for 2 hours to obtain the Co-Si/C@MXene composite anode material;
and 6, soaking the Co-Si/C@MXene composite anode material in the step 5 in 2mol/L hydrochloric acid for 12 hours, and filtering, washing and drying to obtain the Si/C@MXene composite anode material.
The MOF-derived carbon-coated silicon nanoparticles of the invention of example 1-example 3 are limited to the MXene composite anode material with similar performance and parallel effect, and the specific research method and results are shown below by taking example 1 as an example:
the Co/Si@MXene, co-Si/C@MXene and Si/C@MXene negative electrode composite material obtained in the embodiment 1 is assembled into a button cell half cell, and electrochemical performance test is carried out, wherein the button cell assembling steps are as follows: active substance MOF derived carbon coated silicon nano particles are limited to an MXene composite anode material, conductive carbon black and polyvinylidene fluoride, and are added into N-methylpyrrolidone according to the mass ratio of 8:1:1, and are uniformly mixed to prepare electrode slurry; coating the slurry on copper foil with the thickness of 9um, drying the copper foil in a vacuum oven at the temperature of 100 ℃ for 12 hours to prepare a pole piece, filling the pole piece and metal lithium into a button half cell in a glove box filled with argon, and performing performance test on the button cell at the multiplying power of 0.2C by using a LAND cell test system:
FIGS. 1 to 4 are SEM images, charge-discharge graphs, cycle charts and magnification charts of the Co/Si@MXene composite anode material prepared in example 1. From FIG. 1, it can be seen that ZIF-67 coats silicon, since metallic cobalt is the bridge between MOF and MXene, and ZIF-67 then grows in MXene, and finally coats. As a result, the Co/si@mxene composite anode material of example 1 was subjected to a snap-on test, the capacity was maximum at the time of first discharge, and the irreversible loss of capacity was mainly attributed to the generation of an SEI film and the continuous decomposition of an electrolyte in the first cycle. The latter starts to stabilize. Has excellent electrochemical lithium storage stability. The specific capacity after 100 turns was 1400mAh/g. In the magnification graph, the method has better reversibility from low magnification to high magnification to low magnification.
FIGS. 5 to 8 are SEM images, charge-discharge graphs, cycle charts and magnification charts of the Co-Si/C@MXene composite anode material prepared in example 1. From FIG. 5, it can be seen that ZIF-67 coats the silicon and that after carbonization, the surface roughness, MXene and MOF are seen to have some weight loss. As a result, the Co-Si/c@mxene composite anode material of example 1 was subjected to a snap-in test, and the capacity was also maximized at the time of first discharge, and the irreversible loss of capacity was mainly attributed to the generation of the SEI film and the continuous decomposition of the electrolyte in the first cycle. The latter starts to stabilize. Has excellent electrochemical lithium storage stability. The specific capacity after 100 turns was 1401mAh/g. In the magnification graph, the method has better reversibility from low magnification to high magnification to low magnification.
FIGS. 9-12 are SEM images, charge-discharge graphs, cycle charts and magnification charts of the Si/C@MXene composite anode material prepared in example 1. From FIG. 9, it can be seen that ZIF-67 coats the silicon, and after carbonization, it can be seen that the surface roughness, MXene and MOF have some weight loss, and finally the metallic cobalt is washed away by dilute sulfuric acid. As a result, the Si/c@mxene composite anode material of example 1 was subjected to a snap-fit test, and it was found that the specific capacity gradually stabilized after the 10 th and 20 th turns up to 100 th turns, and the specific capacity was 1189mAh/g after 100 th turns in the charge-discharge curve and in the cycle chart. In the magnification graph, the method has better reversibility from low magnification to high magnification to low magnification.
FIGS. 13-14 SEM images of ZIF-67 and MXene.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of the MOF-derived carbon-coated silicon nanoparticle limited MXene composite anode material of the lithium ion battery is characterized by comprising the following steps of:
step 1, dispersing nano silicon and polyvinylpyrrolidone in a solvent, stirring and mixing for 12 hours, and filtering, washing and drying to obtain PVP@Si precursor;
step 2, dispersing PVP@Si and 2-methylimidazole in the step 1 in a solvent, and stirring and mixing for 1h to obtain a mixed solution;
step 3, dispersing cobalt nitrate hexahydrate in the solution, and carrying out ultrasonic treatment for 0.5h to obtain the solution;
step 4, mixing and stirring the mixed solution in the step 2 and the cobalt nitrate solution in the step 3 to obtain a MOF silicon-coated material;
wherein the ratio of the amounts of the substances of 2-methylimidazole and cobalt nitrate hexahydrate is: 2-5;
step 5, mixing the mixed solution obtained in the step 4 with the MXene solution, stirring and mixing the mixture for 24, and filtering, washing and drying the mixture to obtain the Co/Si@MXene composite anode material;
step 6, burning the Co/Si@MXene composite anode material in the step 5 in a tubular furnace for 3 hours to obtain a Co-Si/C@MXene composite anode material;
and 7, carrying out sulfuric acid washing on the Co-Si/C@MXene composite anode material in the step 6 to obtain the Si/C@MXene composite anode material.
2. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: the ratio of the amounts of the substances of the 2-methylimidazole in the step 2 and the cobalt nitrate hexahydrate in the step 3 is: 2-5.
3. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: the particle size of the nano silicon in the step 1 is 60-100nm.
4. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material according to claim 3, which is characterized in that: the dispersing solvent in the step 1 is absolute ethyl alcohol.
5. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: the dispersion solvent in the step 2 is anhydrous methanol.
6. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: in the step 6, when sintering is carried out in a tube furnace, the temperature is increased to 800 ℃ at a heating rate of 3 ℃/min in an inert gas argon or nitrogen environment, and then calcination is carried out for 3 hours.
7. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: in the step 7, when the Co-Si/C@MXene composite anode material is pickled by sulfuric acid, 2mol/L dilute sulfuric acid is used for soaking for 12 hours, and then the Si/C@MXene composite anode material is obtained through filtering, washing and drying.
8. The method for preparing the lithium ion battery MOF-derived carbon-coated silicon nanoparticle limited to the MXene composite anode material, which is characterized by comprising the following steps of: the washing solvents are all absolute methanol.
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| CN117691096B (en) * | 2024-02-04 | 2024-04-09 | 内蒙古工业大学 | Silicon-based composite anode material of all-solid-state lithium battery and preparation method thereof |
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