CN111509216A - Porous silicon film cathode structure of lithium ion battery and preparation method thereof - Google Patents
Porous silicon film cathode structure of lithium ion battery and preparation method thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 54
- 239000010703 silicon Substances 0.000 claims abstract description 54
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 239000002923 metal particle Substances 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000011889 copper foil Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 54
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- 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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Abstract
The invention discloses a preparation method of a porous silicon film cathode structure of a lithium ion battery, which comprises the following steps: (1) preparing a layer of silicon film on the surface of the copper foil; (2) preparing a layer of uniformly distributed catalytic metal particles on the surface of the silicon film; (3) placing the surface covered with the catalytic metal particles in a mixed solution of hydrofluoric acid and an oxidant for corrosion so as to prepare a hole structure on the silicon film; (4) removing catalytic metal particles from the corroded silicon film and drying the silicon film; (5) repeating the steps (1) to (4) n times in sequence. The invention also provides the porous silicon film cathode structure of the lithium ion battery prepared by the method. According to the porous silicon film cathode structure prepared by the invention, the nano holes are uniformly distributed in each layer of silicon film, so that the holes in the whole silicon film cathode are uniformly distributed, the lithium storage expansion effect of the silicon film can be effectively relieved, and the cycle stability of the silicon film cathode structure is improved.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a porous silicon film cathode structure of a lithium ion battery and a preparation method thereof.
Background
Currently, lithium ion batteries are widely used, and in terms of development requirements of lithium ion power batteries, negative electrode materials are required to have the characteristics of high capacity, long service life, high first efficiency, rapid charge and discharge and the like. The theoretical capacity of the existing graphite negative electrode material is 372mAh/g, wherein the commercial graphite negative electrode product reaches about 355mAh/g, and basically no promotion space exists. The theoretical capacity of silicon as the lithium ion battery negative electrode material can reach about 4200mAh/g, and the silicon is rich in the earth crust and is second to oxygen, so the silicon-based lithium ion battery negative electrode material becomes a research hotspot. However, the huge lithium storage expansion effect and poor conductivity of the silicon material limit the exertion of the charge and discharge performance, so that the silicon material cannot be applied on a large scale. Research has found that the expansion effect of the silicon film prepared on the surface of the current collector as the negative electrode can be relieved to a certain extent, and meanwhile, a conductive agent and a binder are not required to be used, so that the cost is saved. However, when the silicon thin film reaches a certain thickness, the lithium storage expansion effect thereof is still a big problem.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention aims to provide a porous silicon film cathode structure of a lithium ion battery and a preparation method thereof.
The invention provides a preparation method of a porous silicon film cathode structure of a lithium ion battery, which comprises the following steps:
preparing a layer of silicon film on the surface of a copper foil;
preparing a layer of uniformly distributed catalytic metal particles on the surface of the silicon film;
placing the surface covered with the catalytic metal particles in a mixed solution of hydrofluoric acid and an oxidant for corrosion so as to prepare a hole structure on the silicon film;
step (4) removing catalytic metal particles from the corroded silicon film and drying the silicon film;
and (5) repeating the steps (1) to (4) n times in sequence.
Further, the method for preparing the silicon film in the step (1) is a chemical vapor deposition method or a physical vapor deposition method;
further, the thickness of the single-layer silicon film is 100-5000 nm;
further, the method for preparing the catalytic metal particles in the step (2) is a metal-assisted chemical corrosion method or a physical vapor deposition method;
further, the catalytic metal particles are silver, copper, gold, platinum and nickel particles;
further, the particle size of the catalytic metal particles is 1-100nm and is smaller than the thickness of the single-layer silicon film;
further, the width of the holes in the step (3) is consistent with the particle size of the catalytic metal particles, the depth of the holes is 1/4-3/4 of the thickness of the single-layer silicon film, and the depth/width ratio of the holes is not less than 5.
Further, the oxidant in the step (3) is hydrogen peroxide, nitric acid, sulfuric acid or hydrochloric acid;
further, the method for removing the catalytic metal particles in the step (4) is to place one side of the silicon film in aqua regia for treatment; if the catalytic metal is silver, the catalyst can also be placed in a mixed solution of ammonia water and hydrogen peroxide for treatment; if the catalytic metal is copper or nickel, the catalyst can also be treated in hydrochloric acid, sulfuric acid or nitric acid solution;
further, the repetition number n in the step (5) is 1-100.
The invention also provides a porous silicon film cathode structure of the lithium ion battery, which is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the porous silicon film negative electrode structure prepared by the invention, the nano holes are uniformly distributed in each layer of silicon film, so that the holes in the whole silicon film negative electrode are uniformly distributed, the lithium storage expansion effect of the silicon film can be effectively relieved, and the cycle stability of the silicon film negative electrode structure is improved.
(2) The particle size of the catalytic metal particles is nano-scale, the inner diameter of the prepared hole is nano-scale, and the depth/width ratio of the prepared hole is not less than 5, so that the hole in the n-1 silicon film is hardly deposited to the silicon film in the process of preparing the n silicon film by a chemical vapor deposition method or a physical vapor deposition method, the uniformity of the porous structure in the invention is ensured, and the lithium storage expansion effect of the silicon film is favorably relieved.
(3) The porous silicon film negative electrode structure prepared by the method is expected to have excellent cycling stability and high specific capacity.
Drawings
Fig. 1 is a schematic diagram of the porous silicon thin film negative electrode structure of the lithium ion battery of the present invention.
Illustration of the drawings: 1-copper foil, 2-silicon film, 3-holes.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a 500nm thick silicon film 2 on the surface of a copper foil 1 by adopting a hot filament chemical vapor deposition method;
(2) then preparing a layer of silver particles with the particle size of 50nm on the surface of the silicon film 2 by adopting a silver-assisted chemical corrosion method;
(3) then, putting the surface covered with the silver particles in a mixed solution of hydrofluoric acid and hydrogen peroxide with a molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of each hole 3 is 300 nm;
(4) removing silver particles by adopting a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3: 1, and drying;
(5) and (4) repeating the steps (1) to (4) for 5 times in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3250mAh/g, and the capacity retention rate of the porous silicon film negative electrode after being cycled for 300 times at 0.5C is 92%.
Example 2
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a 1000nm thick silicon film 2 on the surface of a copper foil 1 by adopting a plasma enhanced chemical vapor deposition method;
(2) then preparing a layer of silver particles with the particle size of 100nm on the surface of the silicon film 2 by adopting a silver-assisted chemical corrosion method;
(3) then, putting the surface covered with the silver particles in a mixed solution of hydrofluoric acid and hydrogen peroxide with a molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of each hole 3 is 700 nm;
(4) removing silver particles by adopting a mixed solution of ammonia water and hydrogen peroxide in a volume ratio of 3: 1, and drying;
(5) repeating the steps (1) to (4) for 3 times in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3210mAh/g, and the capacity retention rate is 90.5% after 0.5C circulation for 300 times.
Example 3
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a 100nm thick silicon film 2 on the surface of a copper foil 1 by adopting a plasma enhanced chemical vapor deposition method;
(2) then preparing a layer of copper particles with the particle size of 10nm on the surface of the silicon film 2 by adopting a copper-assisted chemical corrosion method;
(3) then, putting the surface covered with the copper particles in a mixed solution of hydrofluoric acid and nitric acid with a molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of the holes 3 is 70 nm;
(4) removing copper particles by using a nitric acid solution and drying;
(5) repeating the steps (1) to (4) for 100 times in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3240mAh/g, and the capacity retention rate of the porous silicon film negative electrode after being cycled for 300 times at 0.5C is 91.7%.
Example 4
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a silicon film 2 with the thickness of 5000nm on the surface of a copper foil 1 by adopting a magnetron sputtering method;
(2) then preparing a layer of gold particles with the particle size of 80nm on the surface of the silicon film 2 by adopting a vacuum evaporation method;
(3) then, putting the surface covered with the gold particles in a mixed solution of hydrofluoric acid and hydrochloric acid with the molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of the holes 3 is 3500 nm;
(4) gold particle removal treatment is carried out on the gold-containing composite material by adopting aqua regia solution and drying is carried out;
(5) repeating the steps (1) to (4) for 1 time in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3310mAh/g, and the capacity retention rate is 90.3 percent after 0.5C circulation for 300 times.
Example 5
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a 200nm thick silicon film 2 on the surface of a copper foil 1 by adopting a plasma enhanced chemical vapor deposition method;
(2) then preparing a layer of nickel particles with the particle size of 25nm on the surface of the silicon film 2 by a nickel-assisted chemical corrosion method;
(3) then, putting the surface covered with the nickel particles in a mixed solution of hydrofluoric acid and sulfuric acid with the molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of the holes 3 is 140 nm;
(4) removing nickel particles by using sulfuric acid and drying;
(5) repeating the steps (1) to (4)50 times in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3160mAh/g, and the capacity retention rate is 90.0% after 0.5C circulation for 300 times.
Example 6
The following steps are adopted to prepare the porous silicon film negative electrode structure of the lithium ion battery shown in the figure 1:
(1) firstly, preparing a layer of 1200nm thick silicon film 2 on the surface of a copper foil 1 by adopting a plasma enhanced chemical vapor deposition method;
(2) then preparing a layer of platinum particles with the particle size of 100nm on the surface of the silicon film by adopting a magnetron sputtering method;
(3) then, putting the surface covered with the platinum particles in a mixed solution of hydrofluoric acid and nitric acid with the molar ratio of 1: 1 for corrosion to form holes 3, wherein the depth of the holes 3 is 800 nm;
(4) removing platinum particles by aqua regia solution and drying;
(5) repeating the steps (1) to (4) for 10 times in sequence.
The first discharge capacity of the prepared porous silicon film negative electrode is 3280mAh/g, and the capacity retention rate of the porous silicon film negative electrode after being cycled for 300 times at 0.5C is 91.4%.
The foregoing merely represents preferred embodiments of the invention, which are described in some detail and detail, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes, modifications and substitutions can be made without departing from the spirit of the present invention, and these are all within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a porous silicon film cathode structure of a lithium ion battery is characterized by comprising the following steps:
step (1), preparing a layer of silicon film on the surface of a copper foil;
step (2), preparing a layer of uniformly distributed catalytic metal particles on the surface of the silicon film;
placing the surface covered with the catalytic metal particles in a mixed solution of hydrofluoric acid and an oxidant for corrosion so as to prepare a hole structure on the silicon film;
step (4), removing catalytic metal particles from the corroded silicon film and drying the silicon film;
and (5) repeating the steps (1) to (4) n times in sequence.
2. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the method for preparing the silicon film in the step (1) is a chemical vapor deposition method or a physical vapor deposition method; the method for preparing the catalytic metal particles in the step (2) is a metal-assisted chemical corrosion method or a physical vapor deposition method.
3. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the thickness of the single-layer silicon film is 100-5000 nm.
4. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the catalytic metal particles are silver, copper, gold, platinum and nickel particles.
5. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the particle size of the catalytic metal particles is 1-100 nm.
6. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: and (3) the width of the holes is consistent with the particle size of the catalytic metal particles, the depth of the holes is 1/4-3/4 of the thickness of the single-layer silicon film, and the depth/width ratio of the holes is not less than 5.
7. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the oxidant in the step (3) is hydrogen peroxide, nitric acid, sulfuric acid or hydrochloric acid.
8. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 4, characterized in that: the method for removing the catalytic metal particles in the step (4) is to place one surface of the silicon film in aqua regia for treatment; if the catalytic metal is silver, the catalyst is placed in a mixed solution of ammonia water and hydrogen peroxide for treatment; if the catalytic metal is copper or nickel, the catalyst is treated in a hydrochloric acid, sulfuric acid or nitric acid solution.
9. The preparation method of the porous silicon film negative electrode structure of the lithium ion battery according to claim 1, characterized in that: the repetition number n in the step (5) is 1-100.
10. A porous silicon film cathode structure of a lithium ion battery is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN112820860A (en) * | 2021-01-20 | 2021-05-18 | 江西昌大高新能源材料技术有限公司 | Preparation method of silicon-carbon composite cathode |
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