CN108321368B - Polymer-coated silicon/lithium metasilicate negative electrode material and preparation method thereof - Google Patents
Polymer-coated silicon/lithium metasilicate negative electrode material and preparation method thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 134
- 239000010703 silicon Substances 0.000 title claims abstract description 132
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052912 lithium silicate Inorganic materials 0.000 title claims abstract description 128
- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 64
- 239000011247 coating layer Substances 0.000 claims abstract description 47
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 16
- 229920000767 polyaniline Polymers 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 229920001690 polydopamine Polymers 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 42
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 114
- 229910020489 SiO3 Inorganic materials 0.000 description 18
- 239000002210 silicon-based material Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000012216 screening 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
- H01M4/362—Composites
-
- 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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a polymer-coated silicon/lithium metasilicate cathode material, which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material; the polymer coating layer is formed by one of polypyrrole, polyaniline, polydopamine or polyacrylonitrile. The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps: preparing a silicon/lithium metasilicate composite material and preparing a polymer coating layer. The method has the advantages of simple and feasible process, convenience for large-scale production, high practicability, high reversible capacity of the obtained material, excellent cycle performance and wide application prospect in the aspect of lithium ion battery cathodes.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a polymer-coated silicon/lithium metasilicate cathode material and a preparation method thereof.
Background
The silicon-based material has extremely high specific capacity, for example, the theoretical specific capacity of Si is 4200mAh/g, SiO is 2000mAh/g, and the silicon-based material is an ideal negative electrode material of a high-specific-energy battery. However, the silicon-based material may expand up to 300% in volume during charging and discharging, which generates a large stress to induce the breakage of the silicon-based material particles, thereby causing the pulverization of the material, and finally causing the reduction of the cycle stability of the material. To solve this problem, the academia adopts nano silicon material and constructs compound, and the industry adopts compounding with material (such as graphite) with buffer silicon volume expansion or screening matching adhesive and electrolyte to relieve the volume expansion and circulation stability problems.
At present, the problem of poor cycling stability of the micron-sized silicon-based negative electrode is still in the stage of research and initiation, and no effective method is available.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the polymer-coated silicon/lithium metasilicate negative electrode material and the preparation method thereof, the preparation method has the advantages of simple process, convenience for large-scale production and high practicability, and the obtained negative electrode material can improve the first coulombic efficiency of the material while keeping higher specific capacity and can effectively improve the cycle performance of the material.
The invention provides a polymer-coated silicon/lithium metasilicate cathode material which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
the polymer coating layer is formed by one of polypyrrole, polyaniline, polydopamine or polyacrylonitrile.
Preferably, the weight content of the silicon/lithium metasilicate composite material in the negative electrode material is 95% -98%, and the weight content of the polymer coating layer in the negative electrode material is 2% -5%.
Preferably, its particle size D50 is 5-10 μm.
The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and lithium metal powder, and carrying out ball milling in an argon atmosphere to obtain a silicon/lithium metasilicate composite material;
s2, preparing a polymer coating layer: and uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, and adding an oxidant solution to carry out polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material.
Preferably, in S1, the particle size of the silica is 3 to 10 μm; the particle size of the metal lithium powder is 2-5 mu m; the purity of the argon is 99.99 percent; the atomic ratio of Si and O in the silicon monoxide is n, and n is more than or equal to 1 and less than 2.
Preferably, in S1, the molar ratio of the silica to the lithium metal powder is 8: 1-4: 2.
preferably, in S1, the ball milling time is 1-2h, and the ball milling is mechanical ball milling.
Preferably, in S2, the conductive material is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and carbon fibers; the polymer monomer is one of pyrrole, aniline, dopamine or acrylonitrile; the solvent is one or a mixture of two of ethanol and water.
Preferably, in S2, the oxidant solution is one or more of ferric chloride solution, hydrogen peroxide solution and ammonium persulfate solution.
Preferably, the concentration of the ferric chloride solution is 0.1-1.0 mol/L, the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 3% -10%, and the concentration of the ammonium persulfate solution is 0.1-0.5 mol/L.
The preparation method has the beneficial effects that the polymer-coated silicon/lithium metasilicate cathode material is prepared by adopting a method combining mechanical ball milling reaction and normal-temperature polymerization, in the preparation process of the cathode material, the silicon monoxide is mechanically mixed with the metal lithium powder, and the generated product silicon/lithium metasilicate not only keeps high capacity, but also improves the first coulombic efficiency of the material, meanwhile, L i is formed by reaction in the ball milling process2SiO3Phase, L i can be improved+Ionically conductive and buffer the volume expansion of silicon-based materials. The coating layer is composed of polymer, and can effectively connect and bind the active material particles. Therefore, the silicon/lithium metasilicate anode material coated by the polymer has higher specific capacity and first coulombic efficiency and excellent cycle performanceAnd (3) distinguishing. In addition, the preparation method is simple, safe, low in cost and easy to operate and industrially produce.
Drawings
FIG. 1 is a schematic structural diagram of a polymer-coated silicon/lithium metasilicate negative electrode material according to the present invention;
FIG. 2 is a TEM image of the polymer-coated silicon/lithium metasilicate negative electrode material prepared in example 1 of the present invention;
FIG. 3 is an XRD picture of the polymer-coated silicon/lithium metasilicate anode material prepared in example 1 of the present invention;
fig. 4 is a first charge and discharge of a battery assembled using the polymer-coated silicon/lithium metasilicate anode material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
FIG. 1 is a schematic structural diagram of a polymer-coated silicon/lithium metasilicate negative electrode material according to the present invention; as can be seen from fig. 1, it is composed of a silicon/lithium metasilicate composite material and a polymer coating layer coated on the outside of the silicon/lithium metasilicate composite material.
Example 1
This example shows a polymer-coated silicon/lithium metasilicate cathode material made of a silicon/lithium metasilicate composite material (Si/L i)2SiO3) And a polypyrrole coating layer (P) coated outside the silicon/lithium metasilicate composite material, wherein the silicon/lithium metasilicate composite material accounts for 95 wt%, the polypyrrole coating layer accounts for 5 wt%, and the polypyrrole coating layer comprises [ Si/L i ]2SiO3]0.95/P0.05；
The preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material provided by the embodiment comprises the following steps:
s1, preparation of silicon/lithium metasilicate composite material Si/L i2SiO35.0g of silicon monoxide and 0.5g of lithium metal powder are mechanically ball-milled and mixed for 1 hour under the argon atmosphere to obtain a silicon/lithium metasilicate composite material Si/L i2SiO3；
S2, preparing a polypyrrole coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material in 1.95g S1, 0.05g of conductive material and 200 mu L of pyrrole in 50ml of ethanol, and dropwise adding 6ml of 0.5 mol/L ferric chloride solution for polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material, namely the polypyrrole-coated silicon/lithium metasilicate negative electrode material.
Fig. 2 is a TEM image of the polymer-coated silicon/lithium metasilicate negative electrode material prepared in example 1 of the present invention, and it can be seen from fig. 2 that the core particles (central black region, about 1-1.5 μm) are coated with flocculent polymer coating layer, and the coating layer has rough and uneven surface and abundant nano-structure.
FIG. 3 is an XRD picture of the polymer-coated silicon/lithium metasilicate negative electrode material prepared in example 1 of the present invention, and it can be seen from FIG. 3 that the peak positions of Si appear at around 28.4, 47.3 and 56.1 degrees, whereas L i is2SiO3The diffraction peaks of (a) are around 18.9, 27.0, 33.1, 38.6 and 43.4 deg..
The polypyrrole-coated silicon/lithium metasilicate negative electrode material prepared in this example and a lithium counter electrode were assembled into a button cell, and a first charge and discharge test was performed on the assembled button cell, and the result is shown in fig. 4, and as can be seen from fig. 4, the first discharge specific capacity of the cell assembled by using the polymer-coated silicon/lithium metasilicate negative electrode material prepared in example 1 of the present invention was 2146mAh/g, and the first charge and discharge efficiency was 74.4%.
Example 2
This example shows a polymer-coated silicon/lithium metasilicate cathode material made of a silicon/lithium metasilicate composite material (Si/L i)2SiO3) And a polyaniline coating layer (P) coated outside the silicon/lithium metasilicate composite material, wherein the silicon/lithium metasilicate composite material accounts for 95 wt%, the polyaniline coating layer accounts for 5 wt%, and the polyaniline coating layer comprises [ Si/L i ]2SiO3]0.95/P0.05；
The preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material provided by the embodiment comprises the following steps:
s1, preparation of silicon/lithium metasilicate composite material Si/L i2SiO35.0g of silicon monoxide and 0.5g of lithium metal powder are mechanically ball-milled and mixed for 1 hour under the argon atmosphere to obtain a silicon/lithium metasilicate composite material Si/L i2SiO3；
S2, preparing a polyaniline coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material in 1.95g S1, 0.05g of conductive material and 200 mu L of aniline in 50ml of ethanol, and dropwise adding 6ml of 0.5 mol/L ferric chloride solution for polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material, namely the polyaniline-coated silicon/lithium metasilicate negative electrode material.
The polyaniline-coated silicon/lithium metasilicate negative electrode material prepared in the example and a lithium counter electrode were assembled into a button cell, and the first discharge specific capacity of the cell was 2071mAh/g, and the first charge-discharge efficiency was 68.5%.
Example 3
This example shows a polymer-coated silicon/lithium metasilicate cathode material made of a silicon/lithium metasilicate composite material (Si/L i)2SiO3) And a polypyrrole coating layer (P) coated outside the silicon/lithium metasilicate composite material, wherein the silicon/lithium metasilicate composite material accounts for 98% by weight, the polypyrrole coating layer accounts for 2% by weight, and the polypyrrole coating layer comprises [ Si/L i ]2SiO3]0.98/P0.02；
The preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material provided by the embodiment comprises the following steps:
s1, preparation of silicon/lithium metasilicate composite material Si/L i2SiO35.0g of silicon monoxide and 0.5g of lithium metal powder are mechanically ball-milled and mixed for 0.5h under the argon atmosphere to obtain the silicon/lithium metasilicate composite material Si/L i2SiO3；
S2, preparing a polymer coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material in 1.95g S1, 0.05g of conductive material and 80 mu L of pyrrole in 50ml of ethanol, and dropwise adding 15ml of 0.1 mol/L ammonium persulfate solution for polymerization reaction to obtain the polymer coated silicon/lithium metasilicate negative electrode material, namely the polypyrrole coated silicon/lithium metasilicate negative electrode material.
The polypyrrole-coated silicon/lithium metasilicate negative electrode material prepared in the embodiment and a lithium counter electrode are assembled into a button cell, and the first discharge specific capacity of the cell is 2096mAh/g, and the first charge-discharge efficiency is 71.4%.
Example 4
This example shows a polymer-coated silicon/lithium metasilicate cathode material made of a silicon/lithium metasilicate composite material (Si/L i)2SiO3) And a polyaniline coating layer (P) coated outside the silicon/lithium metasilicate composite material, wherein the silicon/lithium metasilicate composite material accounts for 98 percent by weight, the polyaniline coating layer accounts for 2 percent by weight, and the polyaniline coating layer comprises [ Si/L i ]2SiO3]0.98/P0.02；
The preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material provided by the embodiment comprises the following steps:
s1, preparation of silicon/lithium metasilicate composite material Si/L i2SiO35.0g of silicon monoxide and 0.5g of lithium metal powder are mechanically ball-milled and mixed for 0.5h under the argon atmosphere to obtain the silicon/lithium metasilicate composite material Si/L i2SiO3；
S2, preparing a polymer coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material in 1.95g S1, 0.05g of conductive material and 80 mu L of aniline in 50ml of ethanol, and dropwise adding 15ml of 0.1 mol/L ammonium persulfate solution for polymerization reaction to obtain the polymer coated silicon/lithium metasilicate negative electrode material, namely the polyaniline coated silicon/lithium metasilicate negative electrode material.
The polyaniline-coated silicon/lithium metasilicate negative electrode material prepared in the example and a lithium counter electrode were assembled into a button cell, and the first discharge specific capacity of the cell was found to be 1804mAh/g, and the first charge-discharge efficiency was found to be 54.6%.
Example 5
The invention provides a polymer-coated silicon/lithium metasilicate cathode material which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
wherein the polymer coating layer is formed by polypyrrole.
The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and lithium metal powder, and carrying out ball milling in an argon atmosphere to obtain a silicon/lithium metasilicate composite material;
s2, preparing a polymer coating layer: and uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, and adding an oxidant solution to carry out polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material.
Example 6
The invention provides a polymer-coated silicon/lithium metasilicate cathode material which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
wherein the weight content of the silicon/lithium metasilicate composite material in the negative electrode material is 98 percent, and the weight content of the polymer coating layer in the negative electrode material is 2 percent; the polymer coating layer is formed by polypyrrole; the polymer-coated silicon/lithium metasilicate negative electrode material had a particle size D50 of 5 μm.
The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and metal lithium powder, and carrying out ball milling for 1h in an argon atmosphere to obtain a silicon/lithium metasilicate composite material; wherein the particle size of the silicon monoxide is 3-10 μm; the particle size of the metal lithium powder is 2-5 mu m; the purity of the argon is 99.99 percent; the atomic ratio of Si to O in the silicon monoxide is n, and n is 1; the molar ratio of the silicon monoxide to the metal lithium powder is 8: 1; the ball milling is mechanical ball milling;
s2, preparing a polymer coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, adding an oxidant solution, and carrying out a polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material, wherein the conductive material is a mixture of acetylene black and a carbon nano tube, the mass ratio of the acetylene black to the carbon nano tube is 3:2, the polymer monomer is pyrrole, the solvent is ethanol, the oxidant solution is an iron chloride solution, and the concentration of the iron chloride solution is 0.1 mol/L.
Example 7
The invention provides a polymer-coated silicon/lithium metasilicate cathode material which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
wherein the weight content of the silicon/lithium metasilicate composite material in the negative electrode material is 95%, and the weight content of the polymer coating layer in the negative electrode material is 5%; the polymer coating layer is formed by polyaniline; the particle size D50 of the polymer-coated silicon/lithium metasilicate negative electrode material was 10 μm.
The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and metal lithium powder, and carrying out ball milling for 2 hours in an argon atmosphere to obtain a silicon/lithium metasilicate composite material; wherein the particle size of the silicon monoxide is 3-10 μm; the particle size of the metal lithium powder is 2-5 mu m; the purity of the argon is 99.99 percent; the atomic ratio of Si to O in the silicon protoxide is n, and n is 1.8; the molar ratio of the silicon monoxide to the metal lithium powder is 4: 2; the ball milling is mechanical ball milling;
s2, preparing a polymer coating layer: uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, and adding an oxidant solution to carry out polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material; wherein the conductive material is conductive carbon black; the polymer monomer is aniline; the solvent is water; the oxidant solution is hydrogen peroxide solution; the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 3%.
Example 8
The invention provides a polymer-coated silicon/lithium metasilicate cathode material which consists of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
wherein the weight content of the silicon/lithium metasilicate composite material in the negative electrode material is 97%, and the weight content of the polymer coating layer in the negative electrode material is 3%; the polymer coating layer is formed by polydopamine; the polymer-coated silicon/lithium metasilicate anode material had a particle size D50 of 8 μm.
The invention also provides a preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material, which comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and metal lithium powder, and carrying out ball milling for 1.5h in an argon atmosphere to obtain a silicon/lithium metasilicate composite material; wherein the particle size of the silicon monoxide is 3-10 μm; the particle size of the metal lithium powder is 2-5 mu m; the purity of the argon is 99.99 percent; the atomic ratio of Si to O in the silicon protoxide is n, and n is 1.5; the molar ratio of the silicon monoxide to the metal lithium powder is 5: 1; the ball milling is mechanical ball milling;
s2, preparing a polymer coating layer, namely uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, and adding an oxidant solution to perform a polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material, wherein the conductive material is a mixture of conductive carbon black, graphene and carbon fibers, the mass ratio of the conductive carbon black, the graphene and the carbon fibers is 4:3:2, the polymer monomer is dopamine, the solvent is a mixture of ethanol and water, the volume ratio of the ethanol to the water is 3:2, the oxidant solution is a mixture of an iron chloride solution, a hydrogen peroxide solution and an ammonium persulfate solution, the concentration of the iron chloride solution is 1.0 mol/L, the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 10%, and the concentration of the ammonium persulfate solution is 0.5 mol/L.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The polymer-coated silicon/lithium metasilicate cathode material is characterized by consisting of a silicon/lithium metasilicate composite material and a polymer coating layer coated outside the silicon/lithium metasilicate composite material;
the polymer coating layer is a coating layer formed by one of polypyrrole, polyaniline, polydopamine or polyacrylonitrile;
the preparation method of the polymer-coated silicon/lithium metasilicate negative electrode material comprises the following steps:
s1, preparing a silicon/lithium metasilicate composite material: taking silicon monoxide and lithium metal powder, and carrying out ball milling in an argon atmosphere to obtain a silicon/lithium metasilicate composite material;
s2, preparing a polymer coating layer: uniformly dispersing the silicon/lithium metasilicate composite material, the conductive material and the polymer monomer in the S1 in a solvent, and adding an oxidant solution to carry out polymerization reaction to obtain the polymer-coated silicon/lithium metasilicate negative electrode material;
wherein in S1, the molar ratio of the silicon oxide to the lithium metal powder is 8: 1-4: 2;
wherein, in S1, the ball milling time is 1-2h, and the ball milling is mechanical ball milling.
2. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 1, wherein the silicon/lithium metasilicate composite material is present in the negative electrode material in an amount of 95% to 98% by weight, and the polymer coating layer is present in the negative electrode material in an amount of 2% to 5% by weight.
3. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 1 or 2, wherein the particle size D50 is 5 to 10 μm.
4. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 1 wherein in S1, the particle size of the siliconoxide is 3 to 10 μm; the particle size of the metal lithium powder is 2-5 mu m; the purity of the argon is 99.99 percent; the atomic ratio of Si and O in the silicon monoxide is n, and n is more than or equal to 1 and less than 2.
5. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 1 or 4, wherein in S2, the conductive material is one or more of conductive carbon black, acetylene black, carbon nanotubes, graphene and carbon fibers; the polymer monomer is one of pyrrole, aniline, dopamine or acrylonitrile; the solvent is one or a mixture of two of ethanol and water.
6. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 1 or 4, wherein in S2, the oxidant solution is one or more of a mixture of ferric chloride solution, hydrogen peroxide solution and ammonium persulfate solution.
7. The polymer-coated silicon/lithium metasilicate negative electrode material of claim 6, wherein the concentration of the ferric chloride solution is 0.1-1.0 mol/L, the mass fraction of hydrogen peroxide in the hydrogen peroxide solution is 3% -10%, and the concentration of the ammonium persulfate solution is 0.1-0.5 mol/L.
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