CN115010135B - Two-dimensional silicon nano-sheet for lithium ion battery cathode and preparation method thereof - Google Patents
Two-dimensional silicon nano-sheet for lithium ion battery cathode and preparation method thereof Download PDFInfo
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- CN115010135B CN115010135B CN202210797541.6A CN202210797541A CN115010135B CN 115010135 B CN115010135 B CN 115010135B CN 202210797541 A CN202210797541 A CN 202210797541A CN 115010135 B CN115010135 B CN 115010135B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 104
- 239000010703 silicon Substances 0.000 title claims abstract description 104
- 239000002135 nanosheet Substances 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005530 etching Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000002064 nanoplatelet Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 10
- 239000004576 sand Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a two-dimensional silicon nano sheet for a lithium ion battery cathode and a preparation method thereof. The method mainly aims at the problems that the existing two-dimensional silicon nano-sheet can only be prepared in a small amount in a laboratory through a complex process, and a method for preparing the two-dimensional silicon nano-sheet in a low-energy consumption and large-scale manner is lacked, and provides the following technical scheme: the preparation method comprises the following steps: step one: etching the silicon alloy in an acid solution to obtain porous silicon; step two: the porous silicon is subjected to jet mill to obtain a micron silicon wafer; step three: and sanding the micron silicon wafer under the action of a dispersing agent to obtain the two-dimensional silicon nano-sheet of the lithium ion battery cathode. The preparation method has the advantages of low energy consumption and equipment input, reduces the preparation cost of the two-dimensional silicon nano-sheet, expands the application range of the two-dimensional silicon nano-sheet, and has strong endurance of the lithium ion battery applying the two-dimensional silicon nano-sheet.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a two-dimensional silicon nano sheet for a lithium ion battery cathode and a preparation method thereof.
Background
In the existing energy storage equipment, the lithium ion battery has the advantages of high energy density, small volume, no memory effect, small self-discharge point effect and the like, and has been widely applied to portable electronic equipment and plays an important role in the fields of electric power energy storage systems and aerospace. However, the current commercial lithium ion battery has an energy density of about 150-180 Wh/Kg, which makes it difficult to meet the endurance requirements of consumer electronics, especially electric automobiles.
Therefore, there is an urgent need to develop a lithium ion battery system with high energy density. From the standpoint of the negative electrode material, silicon has the advantages of high theoretical specific capacity (4200 mA h g-1) and low voltage plateau, and is considered to be an ideal negative electrode material for the next generation lithium ion battery. However, the low intrinsic conductivity of silicon and the huge volume change during charge and discharge limit the application of the silicon-based negative electrode in the field of lithium ion batteries, and the modification of the silicon-based negative electrode has very important significance for overcoming the defects.
Currently, there are three types of commonly used modifications to silicon-based cathodes: nanocrystallization, porosification, or recombination with carbon. In theory, the smaller the size of the silicon nano-particles, the smaller the expansion of absolute volume during charge and discharge, so nanocrystallization is a means for solving the expansion of the volume of the silicon anode material from the origin. The methods commonly used in industry to prepare silicon nanoparticles are based on large-size monocrystalline or coarse silicon, with the size being continuously reduced by physical means (e.g. sand milling, ball milling, etc.). However, these methods have some problems, namely, the linkage of a plurality of sand mills or ball mills is required, the energy consumption is high during large-scale production, and the obtained nano particles are generally three-dimensional spherical particles, the absolute volume expansion is reduced in the charge and discharge process, but the isotropic expansion easily causes the breakage of silicon particles, and the stability of the electrode material is reduced.
Recent reports suggest that two-dimensional silicon nanoplatelets can overcome the defects of three-dimensional silicon nanoparticles (Advanced Functional Materials, 2022, 2110046), and that the volume expansion of the axial and radial anisotropy is beneficial to the maintenance of the complete structure of the silicon particles during charge and discharge, improving the cycle life.
However, the preparation of two-dimensional silicon nanoplates generally requires complex chemical processes or sophisticated physical equipment (CVD, PVD, atomic beam cutting, etc.), and can only be prepared in small amounts in a laboratory. At present, a mode for preparing the two-dimensional silicon nano-sheet in a low energy consumption and large scale is still lacking.
Disclosure of Invention
The invention aims at solving the problems that the existing two-dimensional silicon nano-sheet in the background technology can only be prepared in a small amount in a laboratory through a complex process, and a method for preparing the two-dimensional silicon nano-sheet in a low-energy consumption and large-scale manner is lacked, so that the two-dimensional silicon nano-sheet cannot be widely popularized and used, and provides a two-dimensional silicon nano-sheet for a lithium ion battery cathode and a preparation method thereof.
The technical scheme of the invention is as follows: the two-dimensional silicon nano sheet for the lithium ion battery cathode is characterized by being prepared according to the following method, and specifically comprises the following preparation steps:
step one: selecting proper ferrosilicon alloy, and etching the ferrosilicon alloy in 6M hydrochloric acid solution to obtain porous silicon, wherein the etching time is 2-120h, and the etching temperature is 20-80 ℃;
step two: transferring the porous silicon obtained in the first step into an air flow pulverizer to pulverize to obtain a micron silicon wafer, wherein an air source adopted by the air flow pulverizer is compressed air, and the pulverizing treatment time of the air flow pulverizer is 1-24 hours;
step three: dispersing the micron silicon wafer obtained in the step II in a solvent under the action of a dispersing agent, and then performing sanding treatment to obtain a two-dimensional silicon nano-sheet of a lithium ion battery cathode, wherein the solvent selected in the sanding treatment is any one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and acetonitrile, the dispersing agent is polyvinylpyrrolidone, the sanding treatment temperature is 10-50 ℃, the sanding time is 1-24h, the dimension of the obtained two-dimensional silicon nano-sheet is 20-300nm, the thickness is 1-10nm, and the oxygen content is 16.3-40wt%;
the silicon content in the silicon alloy is 1-99%, and the average grain diameter of the silicon alloy is 50 meshes;
the average grain diameter of the micron silicon chip after being crushed by the jet mill is 3-5 mu m, and the thickness is 50nm;
the solid content of the micron silicon chip in the sanding treatment process is 1-50wt% and the content of the dispersing agent is 0.01-1wt%.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention provides a two-dimensional silicon nanoparticle with adjustable size, thickness and oxygen content ratio, which is prepared according to the requirements of an actual lithium ion battery, provides different preparation requirements for adjustment, and is suitable for different application ranges;
2. the preparation method of the two-dimensional silicon nano-sheet is simple and convenient to operate, the reaction conditions are easy to control, the two-dimensional silicon nano-sheet can be prepared in a large scale, the two-dimensional silicon nano-sheet is ensured not to be a product only stored in a laboratory, the raw materials are easy to obtain, the method is simple, the energy consumption is low, the method can be used for large-scale production, and the preparation path of the two-dimensional silicon nano-sheet is expanded;
3. the two-dimensional silicon nano-sheet prepared by the method is applied to the field of lithium ion batteries, and in the charging and discharging process, the expansion of the axial and radial anisotropism enables the two-dimensional silicon nano-sheet to show excellent structural stability and long cycle life, so that the cruising ability of the lithium ion battery is improved;
4. in conclusion, the method for preparing the two-dimensional silicon nano-sheet has low energy consumption and low equipment investment, so that the preparation cost of the two-dimensional silicon nano-sheet is reduced, the preparation way of the two-dimensional silicon nano-sheet is expanded, the problem that the two-dimensional silicon nano-sheet is only prepared in a laboratory is solved, the application range of the two-dimensional silicon nano-sheet is popularized, and the lithium ion battery applying the two-dimensional silicon nano-sheet has strong endurance.
Drawings
FIG. 1 is a flow chart of a method of preparing two-dimensional silicon nanoplatelets for use in a lithium ion battery anode;
FIG. 2 is a scanning electron microscope image of a micrometer silicon wafer provided in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a two-dimensional silicon nanoplate provided in example 1 of the present invention;
FIG. 4 is a dynamic light scattering diagram of a two-dimensional silicon nanoplatelet provided in example 1 of the present invention;
FIG. 5 is a transmission electron microscope image of a two-dimensional silicon nanoplate provided in example 1 of the present invention;
FIG. 6 is a high resolution transmission electron microscope image of a two-dimensional silicon nanoplatelet provided in example 1 of the present invention;
FIG. 7 is an X-ray diffraction pattern of a two-dimensional silicon nanoplatelet provided in example 1 of the present invention;
FIG. 8 is an EDX of a two-dimensional silicon nanoplatelet provided in example 1 of the present invention;
fig. 9 is a schematic diagram of a charge-discharge curve of the first turn of the two-dimensional silicon nanoplatelets provided in embodiment 1 of the present invention;
fig. 10 is a schematic view of a cyclic charge-discharge curve of a two-dimensional silicon nanoplatelet according to embodiment 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the attached drawings and specific embodiments.
The two-dimensional silicon nano sheet for the lithium ion battery cathode is prepared according to the following method, and specifically comprises the following preparation steps:
step one: selecting proper ferrosilicon alloy, and etching the ferrosilicon alloy in an acid solution to obtain porous silicon;
step two: transferring the porous silicon obtained in the first step into an airflow crusher to be crushed to obtain a micron silicon wafer;
step three: and step two, dispersing the obtained micron silicon wafer in a solvent under the action of a dispersing agent, and performing sanding treatment to obtain the two-dimensional silicon nano-sheet of the lithium ion battery cathode.
Wherein the selected ferrosilicon is ferrosilicon, and the acidic solution used for etching is hydrochloric acid.
Example 1
As shown in fig. 1-10, a ferrosilicon alloy with the grain size of 50 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, and then transferred into a jet mill, and crushed for 3 hours at room temperature by taking compressed air as an air source, so as to obtain a micron silicon wafer with the size of 3-5 mu M. Dispersing 100g of micron silicon wafer in 900g of ethanol (solid content is 10wt%) and then adding 0.1g of polyvinylpyrrolidone, and sanding for 7h at room temperature to obtain a two-dimensional silicon nano-sheet with the size of 300nm, the thickness of 10nm and the oxygen content of 16.3wt%;
in this example, FIG. 2 shows that the size of a two-dimensional silicon wafer after jet milling is 3-5 μm and the thickness is 50nm by a scanning electron microscope of the obtained micrometer silicon wafer.
FIG. 3 is a scanning electron microscope showing a two-dimensional silicon nanosheet with a product size of 300nm and a thickness of 10nm after sanding.
FIG. 4 is a dynamic light scattering diagram of the obtained two-dimensional silicon nanoplatelets, showing that the particle size distribution of the two-dimensional silicon nanoplatelets is concentrated and the average particle size is 260nm.
Fig. 5 is a transmission electron microscope image of the resulting two-dimensional silicon nanoplatelets, showing the nanoplatelet structure of the material, which is a typical two-dimensional material.
Fig. 6 is a high resolution transmission electron microscopy image of the resulting two-dimensional silicon nanoplatelets showing that the material has a highly crystalline structure, but some amorphous structure is observed on the outermost side of the nanoplatelets, indicating that the nanoplatelets contain a certain amount of oxygen.
Fig. 7 is a powder X-ray diffraction pattern of the obtained two-dimensional silicon nanoplatelets, which corresponds to X-ray diffraction peaks of elemental silicon one by one.
Fig. 8 is an EDX graph of the obtained two-dimensional silicon nanoplatelets, showing that the material contains a certain amount of oxygen.
Fig. 9 is a first charge-discharge curve of the resulting two-dimensional silicon nanoplatelets, showing a first coulombic efficiency of the material of about 83.4%.
FIG. 10 is a graph showing the cycling charge and discharge curves of the obtained two-dimensional silicon nanoplatelets, wherein the capacity retention of charge and discharge for 20 cycles is still 75% at 1000 mAh-1.
Example two
As shown in FIG. 1, a ferrosilicon alloy with the grain size of 50 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, then transferred into a jet mill, and crushed for 3 hours at room temperature by taking argon as a gas source, thus obtaining a micron silicon wafer with the size of 3-5 mu M. 100g of micron silicon wafer is taken to be dispersed in 900g of ethanol (the solid content is 10 wt%), then 0.1g of polyvinylpyrrolidone is added, and sand milling is carried out for 7 hours at room temperature, thus obtaining the two-dimensional silicon nano-sheet with the size of 300nm and the thickness of 10nm and without oxygen.
Example III
As shown in FIG. 1, a ferrosilicon alloy with the grain size of 20 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, and then transferred into a jet mill, and crushed for 3 hours at room temperature by taking compressed air as an air source, so as to obtain a micron silicon wafer with the size of 5-10 mu M. 100g of micron silicon wafer is dispersed in 900g of ethanol (the solid content is 10 wt%), then 0.1g of polyvinylpyrrolidone is added, and sand milling is carried out for 7 hours at room temperature, thus obtaining the two-dimensional silicon nano-sheet with the size of 600nm, the thickness of 10nm and the oxygen content of 16.3 wt%.
Example IV
As shown in FIG. 1, a ferrosilicon alloy with a grain size of 50 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, and then transferred into a jet mill, and crushed for 10 hours at room temperature by taking compressed air as an air source, so as to obtain a micron silicon wafer with a size of 1-3 mu M. 100g of micron silicon wafer is dispersed in 900g of ethanol (the solid content is 10 wt%), then 0.1g of polyvinylpyrrolidone is added, and sand milling is carried out for 7 hours at room temperature, thus obtaining the two-dimensional silicon nano-sheet with the size of 200nm, the thickness of 10nm and the oxygen content of 20.5 wt%.
Example five
As shown in FIG. 1, a ferrosilicon alloy with the grain size of 50 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, and then transferred into a jet mill, and crushed for 3 hours at room temperature by taking compressed air as an air source, so as to obtain a micron silicon wafer with the size of 3-5 mu M. 100g of micron silicon wafer is dispersed in 900g of ethanol (the solid content is 10 wt%), then 0.1g of polyvinylpyrrolidone is added, and sanding is carried out for 2 hours at room temperature, thus obtaining the two-dimensional silicon nano-sheet with the size of 800nm, the thickness of 30nm and the oxygen content of 16.3 wt%.
Example six
As shown in FIG. 1, a ferrosilicon alloy with the grain size of 50 meshes is placed in a 6M hydrochloric acid solution, etched for 10 hours at room temperature, separated and dried, and then transferred into a jet mill, and crushed for 3 hours at room temperature by taking compressed air as an air source, so as to obtain a micron silicon wafer with the size of 3-5 mu M. 100g of micron silicon wafer is dispersed in 900g of acetonitrile (solid content 10 wt%) and then 0.1g of polyvinylpyrrolidone is added, and sand milling is carried out for 7 hours at room temperature, thus obtaining the two-dimensional silicon nano-sheet with the size of 300nm and the thickness of 10nm and without oxygen.
From the first to sixth embodiments, it can be known that the two-dimensional silicon nanosheets provided in the present solution are controllable in preparation size, thickness and oxygen content, and suitable for mass production with different requirements.
And the two-dimensional silicon nano-sheet prepared by the method is used as a lithium ion battery cathode, and the performance is detected to obtain the following conclusion: the two-dimensional silicon nano-sheet shows excellent performance when being used as a negative electrode of a lithium ion battery, and the capacity of the two-dimensional silicon nano-sheet still maintains 75% after the two-dimensional silicon nano-sheet is cycled for 20 times under the current density of 1000 mA/g, which is far greater than the capacity of three-dimensional silicon nano-particles with the same size. Therefore, the two-dimensional silicon nano-sheet prepared by the scheme has outstanding characteristics and is suitable for popularization and use.
The above-described embodiments are merely a few preferred embodiments of the present invention, and many alternative modifications and combinations of the above-described embodiments will be apparent to those skilled in the art based on the technical solutions of the present invention and the related teachings of the above-described embodiments.
Claims (1)
1. The two-dimensional silicon nano sheet for the lithium ion battery cathode is characterized by being prepared according to the following method, and specifically comprises the following preparation steps:
step one: selecting proper ferrosilicon alloy, and etching the ferrosilicon alloy in 6M hydrochloric acid solution to obtain porous silicon, wherein the etching time is 2-120h, and the etching temperature is 20-80 ℃;
step two: transferring the porous silicon obtained in the first step into an air flow pulverizer to pulverize to obtain a micron silicon wafer, wherein an air source adopted by the air flow pulverizer is compressed air, and the pulverizing treatment time of the air flow pulverizer is 1-24 hours;
step three: dispersing the micron silicon wafer obtained in the step II in a solvent under the action of a dispersing agent, and then performing sanding treatment to obtain a two-dimensional silicon nano-sheet of a lithium ion battery cathode, wherein the solvent selected in the sanding treatment is any one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and acetonitrile, the dispersing agent is polyvinylpyrrolidone, the sanding treatment temperature is 10-50 ℃, the sanding time is 1-24h, the dimension of the obtained two-dimensional silicon nano-sheet is 20-300nm, the thickness is 1-10nm, and the oxygen content is 16.3-40wt%;
the silicon content in the ferrosilicon alloy is 1-99%, and the average grain diameter of the ferrosilicon alloy is 50 meshes;
the average grain diameter of the micron silicon chip after being crushed by the jet mill is 3-5 mu m, and the thickness is 50nm;
the solid content of the micron silicon chip in the sanding treatment process is 1-50wt% and the content of the dispersing agent is 0.01-1wt%.
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| WO2014102219A1 (en) * | 2012-12-24 | 2014-07-03 | Solvay Sa | Silicon nanosheet and preparing method of the same |
| CN111211314A (en) * | 2020-02-25 | 2020-05-29 | 上海旦元新材料科技有限公司 | Carbon-coated porous silicon-carbon composite material and preparation method thereof |
| CN111952559A (en) * | 2020-07-29 | 2020-11-17 | 华南理工大学 | Silicon-carbon microsphere composite material self-assembled by two-dimensional silicon nanosheets, preparation method and application thereof in lithium ion battery cathode material |
| CN113611837A (en) * | 2021-08-03 | 2021-11-05 | 辽宁石油化工大学 | Nano silicon composite material, preparation method and application thereof |
| CN113924668A (en) * | 2019-05-08 | 2022-01-11 | 香港商Eo细胞有限公司 | Silicon Carbon Nanocomposite (SCN) material, process for its manufacture and its use in anode electrodes for lithium ion batteries |
| CN114628661A (en) * | 2020-12-11 | 2022-06-14 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
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