CN111799460A - Method for preparing boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste - Google Patents
Method for preparing boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste Download PDFInfo
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- CN111799460A CN111799460A CN202010696789.4A CN202010696789A CN111799460A CN 111799460 A CN111799460 A CN 111799460A CN 202010696789 A CN202010696789 A CN 202010696789A CN 111799460 A CN111799460 A CN 111799460A
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- 239000002184 metal Substances 0.000 title claims abstract description 152
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 152
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 78
- 239000010703 silicon Substances 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 52
- 238000005520 cutting process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 83
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 76
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 44
- 239000011863 silicon-based powder Substances 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
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- 239000000203 mixture Substances 0.000 claims description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
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- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
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- 239000010439 graphite Substances 0.000 claims description 11
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002296 pyrolytic carbon Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011646 cupric carbonate Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
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- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 benzene hydrocarbon Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 1
- 239000005720 sucrose Substances 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
-
- 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
-
- 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
- C01B32/00—Carbon; Compounds thereof
-
- 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
- C01B33/037—Purification
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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 a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste. The method comprises the steps of removing impurities from cut silicon waste, carrying out metal-assisted etching treatment to obtain a nano metal/porous silicon composite material, mixing the nano metal/porous silicon composite material with a boron source, carrying out high-temperature treatment to enable boron to form substitutional doping on silicon, and compounding the silicon-doped displacement type doping with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode. According to the invention, the volume expansion of silicon can be relieved by adding the porous structure of silicon and the carbon material, the circulation stability is increased, the metal particles are physically compounded with the silicon on the surface of the silicon substrate and boron is chemically doped on the silicon on the atomic scale to realize the synergistic effect, and finally the intrinsic conductivity and the electrochemical activity of the silicon-based composite material are improved, so that the boron-doped nano metal/silicon-carbon composite negative electrode material with high charge-discharge specific capacity and long cycle life is prepared.
Description
Technical Field
The invention relates to a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste, belonging to the technical field of new energy materials and electrochemistry.
Background
At present, most commercial lithium ion batteries still use graphite materials as negative electrode materials, and the graphite materials have good cycling stability but relatively low specific capacity. The silicon-based negative electrode material has high safety of 4200mAhg-1The upper limit of the amount of silicon that can be developed is very high, but silicon produces very severe volume effects during lithiation: (>300%) to make the silicon material be crushed and unstable in charging and discharging circulationResulting in a rapid decay of the electrode capacity. At present, most of the problems of the silicon cathode are solved by silicon-carbon compounding, but the problems of low intrinsic conductivity of the silicon cathode, low first coulombic efficiency of a battery, high irreversible capacity and the like cannot be solved by the silicon-carbon compounding.
With the development of solar energy technology, more and more solar energy devices are put into use, and in the production of the solar energy devices, a diamond wire multi-wire cutting process is mostly adopted for cutting silicon. However, during the cutting process, about 40% of high-purity silicon material enters into the cutting slurry in the form of sawdust, so that a large amount of silicon material is lost. The part of cutting waste is recycled, so that not only can the secondary utilization of resources be realized, but also certain economic benefits can be brought.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cut silicon waste, namely, the cut silicon waste is subjected to metal-assisted etching treatment after impurity removal to obtain a nano metal/porous silicon composite material, the nano metal/porous silicon composite material is subjected to high-temperature treatment after being mixed with a boron source, so that boron forms substitutional doping on silicon, and then the boron-doped nano metal/porous silicon-carbon composite cathode is compounded with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode; according to the invention, the volume expansion of silicon can be relieved by adding the porous structure of silicon and the carbon material, the circulation stability is increased, the metal particles are physically compounded with the silicon on the surface of the silicon substrate and boron is combined with the silicon to realize the chemical doping synergistic effect on the silicon on the atomic scale, and finally the improvement of the intrinsic conductivity and the improvement of the electrochemical activity of the silicon-based composite material are realized, so that the boron-doped nano metal/silicon carbon composite negative electrode material with high charge-discharge specific capacity and long cycle life is prepared.
A method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution under the stirring condition, carrying out solid-liquid separation, and washing the solid with deionized water until the washing liquid is neutral to obtain purified silicon powder;
(2) placing the purified silicon powder obtained in the step (1) in an HF-metal salt-alcohol solution system for metal-assisted etching treatment, ultrasonically rinsing by using deionized water, carrying out solid-liquid separation, drying the solid in vacuum, and grinding to obtain a nano metal/porous silicon composite material;
(3) uniformly mixing the nano metal/porous silicon composite material obtained in the step (2) with a boron source to obtain a mixture, and treating the mixture at the constant temperature of 400-1200 ℃ in a protective atmosphere for 0.5-12h to obtain a boron-doped nano metal/porous silicon composite material;
(4) soaking the boron-doped nano metal/porous silicon composite material obtained in the step (3) in an alkali solution, performing solid-liquid separation, performing vacuum drying on the solid, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material;
(5) and (4) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode.
The mass concentration of the alkali in the alkali-alcohol solution in the step (1) is 0.1-30%, and the alkali is NaOH, KOH or Ba (OH)2、Ca(OH)2One or more alcohols selected from methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the soaking and purifying treatment time is 1-300 min.
In the step (2), the concentration of HF, the concentration of metal salt and the concentration of alcohols in the HF-metal salt-alcohol solution system are respectively 0.1-20 mol/L, 0.05-5 mol/L and 0.1-20 mol/L; the metal salt is one or more of silver salt, copper salt and nickel salt, the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the purified silicon powder is (10-100) to 1.
Further, the silver salt is AgNO3、Ag2SO4Or Ag2CO3Copper salt being Cu (NO)3)2、CuSO4Or CuCO3The nickel salt is Ni (NO)3)2、NiSO4Or NiCO3。
Preferably, the temperature of the metal auxiliary etching treatment in the step (2) is 1-100 ℃, and the time of the metal auxiliary etching treatment is 1-600 min.
The boron source in the step (3) is one or more of boric acid, boron oxide, boron nitride, trimethyl borate, tripropyl borate, boron tribromide and diborane, and the protective atmosphere is argon or nitrogen.
The alkali solution in the step (4) is KOH solution, Ba (OH)2Solution, NaOH solution, Ca (OH)2One or more of the solutions.
The concentration of the aqueous alkali in the step (4) is 0.1-10 mol/L, the soaking temperature is 1-100 ℃, and the soaking time is 1-120 min.
The mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is 1-20%, and when the nano metal/porous silicon composite material and the boron source are uniformly mixed in the step (2), the adding amount of the boron source is slightly higher than the calculated amount.
The carbon material is one or more of graphite, a carbon nano tube, graphene and pyrolytic carbon, the pyrolytic carbon is one or more of polydopamine, resorcinol-formaldehyde resin, polyvinylpyrrolidone, saccharide materials and aromatic compounds, and the mass fraction of the carbon material in the boron-doped nano metal/porous silicon carbon composite negative electrode is 1-50%.
Preferably, the saccharide is one or more of sucrose, glucose, glycogen and cellulose, and the aromatic compound is benzene hydrocarbon or mono-benzene aromatic hydrocarbon.
The invention has the beneficial effects that:
(1) the diamond wire cutting silicon waste is used as a raw material, so that the raw material source is wide and the price is low; the waste materials are dried, crushed, cleaned, subjected to impurity removal and the like, and are used as silicon-based negative electrode materials of the lithium ion battery, so that the material preparation cost is reduced;
(2) according to the invention, a metal-assisted etching method is adopted to etch silicon into porous silicon, so that the volume expansion of a silicon cathode in the charge-discharge cycle process is effectively relieved, and the cycle stability of the lithium ion battery is increased; the composite material is mixed with a boron source and then is subjected to high-temperature treatment, so that the boron forms substitutional doping on silicon, and the intrinsic conductivity and the electrochemical activity of the silicon material can be improved by the doping of the boron;
(3) according to the invention, the metal particles are physically compounded with silicon on the surface of a silicon substrate and boron is combined with the silicon to realize the synergistic effect of chemical doping on the silicon on the atomic scale, so that the intrinsic conductivity of the silicon-based composite material is improved and the electrochemical activity is improved; the addition of the porous structure of silicon and the later-stage carbon material effectively relieves the volume expansion of the silicon negative electrode in the charging and discharging processes, so that the boron-doped nano metal/porous silicon carbon composite material has higher charging and discharging specific capacity and longer cycle life when being used as the negative electrode material of the lithium ion battery.
Drawings
FIG. 1 is a graph of the cycle performance at 1C rate of a half-cell assembled from raw silicon waste, nano-metal Ag/porous silicon carbon composite, and boron-doped nano-metal Ag/porous silicon carbon composite in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a diamond wire-cut silicon scrap of example 1;
FIG. 3 is a graph of the HF-AgNO passage of the cut silicon scrap of example 13-Scanning Electron Microscopy (SEM) images of the methanol solution system after treatment;
FIG. 4 is a graph of example 2 cut silicon scrap through HF-CuNO3Scanning Electron Microscopy (SEM) images of the methanol solution system after treatment.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-ethanol solution) for 180min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 10 percent,
(2) step (1)) The purified silicon powder is placed in an HF-metal salt-alcohol solution system (HF-AgNO)3-methanol solution system) and at a temperature of 60 ℃ carrying out metal Ag auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Ag/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO)3-methanol solution system) and purified silicon powder with the liquid-solid ratio mL to g of 35:1, HF-AgNO3HF concentration in the methanol solution system of 3.5mol/L, AgNO3The concentration is 0.1mol/L, and the methanol concentration is 3.5 mol/L;
(3) mixing the nano metal Ag/porous silicon composite material obtained in the step (2) with a boron source (B)2O3) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at constant temperature to obtain the boron-doped nano metal Ag/porous silicon composite material;
(4) immersing the boron-doped nano metal Ag/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal Ag/porous silicon composite material is about 5 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (graphite) to obtain a boron-doped nano metal Ag/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano Ag/porous silicon-carbon composite negative electrode is 30%;
the cycle performance curve of the half-cell assembled by the boron-doped nano metal Ag/porous silicon carbon composite cathode in the embodiment is shown in figure 1, compared with a pure silicon cathode and a nano metal Ag/porous silicon carbon composite cathode, the boron-doped nano metal Ag/porous silicon carbon composite cathode has better cycle stability, the first discharge specific capacity is 3300mAh/g under the multiplying power of 1C, and the capacity of more than 1600mAh/g is reserved after 50 times of cycle, which indicates that the electrochemical activity of the composite material is improved by the doping of boron, and the electrochemical performance of the composite material is improved; in the embodiment, a Scanning Electron Microscope (SEM) image of the cut silicon waste is shown in fig. 2, and it can be seen that the cut silicon waste has a large size and a non-uniform particle size distribution, and has a strip-shaped structure; in the embodiment, a Scanning Electron Microscope (SEM) image of porous silicon formed by the cutting silicon waste through Ag-assisted etching is shown in fig. 3, and it can be seen that the particle size of the material is significantly reduced, the strip-shaped structure is no longer present, and the porous structure can be seen on the silicon particles.
Example 2: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-methanol solution) for 150min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 15 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-CuNO)3-methanol solution system) and at a temperature of 60 ℃ carrying out metal Cu auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 60 ℃ for vacuum drying, and grinding to obtain the nano metal Cu/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-CuNO)3A methanol solution system) and the purified silicon powder have a liquid-solid ratio of mL to g of 10:1, and HF-CuNO3HF concentration in the methanol solution system 10mol/L, CuNO3The concentration is 5mol/L, and the methanol concentration is 10 mol/L;
(3) mixing the nano metal Cu/porous silicon composite material obtained in the step (2) with a boron source (B)2O3) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at a constant temperature to obtain the boron-doped nano metal Cu/porous silicon composite material;
(4) immersing the boron-doped nano metal Cu/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 5mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 20 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal Cu/porous silicon composite material obtained in the step (4) and a carbon material (graphite) to obtain a boron-doped nano metal Cu/porous silicon-carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Cu/porous silicon-carbon composite negative electrode is 25%;
in the embodiment, a scanning electron microscope image of the material after the silicon waste material is subjected to the Cu-assisted etching is shown in FIG. 4, and it can be seen that the particle size of the material after the Cu-assisted etching is obviously reduced and the particle size distribution is relatively uniform; after the boron-doped nano metal Cu/porous silicon-carbon composite cathode in the embodiment is assembled into a half-cell, the cycle performance of the half-cell is tested, the initial discharge specific capacity is 2322mAh/g, the capacity of 1230mAh/g is still remained after the half-cell is cycled for 100 times under the multiplying power of 0.5C, and the reduction of the capacity is attributed to the fact that CuNO is used for metal-assisted etching3Too high a concentration results in a large amount of copper remaining in the composite, resulting in a capacity fade; but compared with a pure silicon cathode, the composite material has better cycle stability under the condition of high-rate charge and discharge current.
Example 3: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (NaOH-methanol solution) for 200min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of NaOH in the alkali-alcohol solution (NaOH-methanol solution) is 20 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-NiNO)3-methanol solution system) and at a temperature of 70 ℃ for 100min, ultrasonically rinsing with deionized water until the washing solution is neutralCarrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-NiNO)3-methanol solution system) and the liquid-solid ratio mL/g of the purified silicon powder is 100:1, and HF-NiNO3HF concentration in the methanol solution system of 20mol/L, NiNO3The concentration is 2.5mol/L, and the methanol concentration is 20 mol/L;
(3) mixing the nano metal Ni/porous silicon composite material obtained in the step (2) with a boron source (B)2O3) Uniformly mixing to obtain a mixture, and treating the mixture at 900 ℃ in a nitrogen atmosphere for 6 hours at constant temperature to obtain the boron-doped nano metal Ni/porous silicon composite material;
(4) immersing the boron-doped nano metal Ni/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 90 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 10mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 10 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal Ni/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ni/porous silicon-carbon composite negative electrode is 50%.
After the boron-doped nano metal Ni/porous silicon-carbon composite cathode is assembled into a half-cell, the cycle performance of the half-cell is tested, the initial discharge specific capacity is 1840mAh/g, and the capacity of 1500mAh/g is still reserved after the half-cell is cycled for 100 times under the multiplying power of 0.5C; the reason that the initial specific discharge capacity of the material is lower is that the mass fraction of the graphite added into the material is 50 percent, and the specific capacity of the whole composite material is reduced due to the addition of a large amount of carbon materials; however, the addition of a large amount of graphite improves the cycle stability of the composite.
Example 4: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-ethanol solution) for 120min at room temperature under the condition of stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-ethanol solution) is 30 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-AgNO)3-Cu(NO3)2-ethanol solution system) and at a temperature of 80 ℃ carrying out cooperative auxiliary etching treatment of metal Ag and Cu for 120min, ultrasonically rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying and grinding to obtain the nano metal Ag/Cu/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO)3-Cu(NO3)2-ethanol solution system) and the liquid-solid ratio mL/g of the purified silicon powder is 40:1, and HF-AgNO3-Cu(NO3)2HF concentration in the ethanol solution system of 0.5mol/L, AgNO3The concentration is 0.05mol/L, Cu (NO)3)2The concentration is 0.05mol/L, and the ethanol concentration is 3.5 mol/L;
(3) mixing the nano metal Ag/Cu/porous silicon composite material obtained in the step (2) with a boron source (H)3BO3) Adding the mixture into ethanol, uniformly mixing the mixture in a liquid phase to obtain a mixture, and treating the mixture at the temperature of 1100 ℃ in a nitrogen atmosphere at a constant temperature for 8 hours to obtain the boron-doped nano metal Ag/Cu/porous silicon composite material;
(4) immersing the boron-doped nano metal Ag/Cu/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 90 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 5mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 5 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal Ag and Cu/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ag and Cu/porous silicon-carbon composite negative electrode is 20%.
In the embodiment, the cycle performance of the half-cell assembled by the boron-doped nano metal Ag and Cu/porous silicon-carbon composite cathode is tested, the initial specific discharge capacity is 3200mAh/g, and the capacity of 1799mAh/g is still reserved after the half-cell is cycled for 100 times under the multiplying power of 0.5C; ag. Compared with single metal etching, the Cu common etching has the advantages that the grain size distribution of etched silicon is more uniform, and more holes are etched on the silicon, so that the specific surface area of the composite material is larger, and the charge-discharge specific capacity of the composite material is improved.
Example 5: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-ethanol solution) for 300min at room temperature under the condition of stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-ethanol solution) is 10 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-AgNO)3-Ni(NO3)2-ethanol solution system) and at a temperature of 80 ℃ carrying out cooperative auxiliary etching treatment on the metal Ag and Ni for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying and grinding to obtain the nano metal Ag/Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-AgNO)3-Ni(NO3)2-ethanol solution system) and purified silicon powder, wherein the liquid-solid ratio mL/g of the purified silicon powder is 35:1, and HF-AgNO is3-Ni(NO3)2HF concentration in the ethanol solution system of 0.1mol/L, AgNO3The concentration is 0.1mol/L, Ni (NO)3)2The concentration is 0.1mol/L, and the ethanol concentration is 0.1 mol/L;
(3) mixing the nano metal Ag/Ni/porous silicon composite material obtained in the step (2) with a boron source (B)2O3And H3BO3) Grinding and uniformly mixing to obtain a mixture, and treating the mixture at the temperature of 1100 ℃ for 6 hours in a nitrogen atmosphere at constant temperature to obtain the boron-doped nano metal Ag/Ni/porous silicon composite material; wherein B is2O3And H3BO3The mass ratio of (A) to (B) is 1: 1;
(4) immersing the boron-doped nano metal Ag/Ni/porous silicon composite material obtained in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 0.1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 1 percent;
(5) ball-milling and uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) and a carbon material (carbon nano tube) to obtain a boron-doped nano metal Ag and Ni/porous silicon carbon composite cathode; wherein the mass fraction of graphite in the boron-doped nano metal Ag and Ni/porous silicon-carbon composite negative electrode is 30%.
In the embodiment, the boron-doped nano metal Ag and Ni/porous silicon-carbon composite cathode is assembled into a half-cell and then tested for cycle performance, the initial specific discharge capacity is 2500mAh/g, and the capacity of 900mAh/g is still remained after 100 cycles under the multiplying power of 0.5C; the reduction in the electrochemical performance of the material is due to the HF-AgNO3-Ni(NO3)2The concentration of HF in an ethanol solution system is too low, so that silicon is not well etched into a porous structure, and meanwhile, the boron doping mass fraction is only 1%, so that the improvement effect on the electrochemical performance of the composite material is limited.
Example 6: a method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste comprises the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution (KOH-methanol solution) for 180min under the conditions of room temperature and stirring, carrying out solid-liquid separation, and washing the solid with deionized water for multiple times until the washing liquid is neutral to obtain purified silicon powder; wherein the mass concentration of KOH in the alkali-alcohol solution (KOH-methanol solution) is 15 percent;
(2) putting the purified silicon powder obtained in the step (1) into an HF-metal salt-alcohol solution system (HF-CuNO)3-Ni(NO3)2-propanol solution system) and at a temperature of 80 ℃ carrying out metal Cu and Ni synergistic auxiliary etching treatment for 120min, carrying out ultrasonic rinsing by using deionized water until the washing solution is neutral, carrying out solid-liquid separation, placing the solid at a temperature of 80 ℃ for vacuum drying, and grinding to obtain the nano metal Cu/Ni/porous silicon composite material; wherein the HF-metal salt-alcohol solution system (HF-CuNO)3-Ni(NO3)2-propanol solution system) and purified silicon powder with the liquid-solid ratio mL/g of 40:1, and HF-CuNO3-Ni(NO3)2HF concentration in the propanol solution system was 0.5mol/L, CuNO3The concentration is 0.05mol/L, Ni (NO)3)2The concentration is 0.05mol/L, and the concentration of propanol is 0.5 mol/L;
(3) mixing the nano metal Cu/Ni/porous silicon composite material obtained in the step (2) with a boron source (B)2O3And H3BO3) Grinding and uniformly mixing to obtain a mixture, and treating the mixture at the temperature of 1100 ℃ for 8 hours in a nitrogen atmosphere at constant temperature to obtain the boron-doped nano metal Cu/Ni/porous silicon composite material; wherein B is2O3And H3BO3The mass ratio of (A) to (B) is 1: 1.5;
(4) immersing the boron-doped nano metal Cu/Ni/porous silicon composite material in the step (3) into an alkali solution (NaOH solution), soaking at the temperature of 25 ℃ for 60min to remove redundant impurities such as silicon dioxide, boron oxide and the like in the composite material, carrying out solid-liquid separation, placing the solid at the temperature of 80 ℃ for vacuum drying, and grinding to obtain the high-purity boron-doped nano metal/porous silicon composite material; wherein the concentration of the NaOH solution is 1mol/L, and the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is about 20 percent;
(5) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with glucose, and then placing the mixture in a tubular furnace to perform carbon coating on the composite material at the temperature of 600 ℃ in a nitrogen atmosphere by using glucose pyrolytic carbon as a carbon source to obtain a boron-doped nano metal Cu and Ni/porous silicon carbon composite cathode; wherein the mass fraction of the pyrolytic carbon in the boron-doped nano metal Cu and Ni/porous silicon-carbon composite negative electrode is 40%.
After the boron-doped nano metal Cu and Ni/porous silicon-carbon composite cathode is assembled into a half-cell, the cycle performance of the half-cell is tested, the initial discharge specific capacity is 2100mAh/g, and the capacity of 1600mAh/g is still reserved after the half-cell is cycled for 100 times under the multiplying power of 0.5C; the composite material has good electrochemical performance, and the initial discharge specific capacity is lower because the composite material contains 40% of carbon by mass fraction, but the addition of the carbon improves the cycle stability of the whole material.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing a boron-doped nano metal/porous silicon-carbon composite cathode based on cutting silicon waste is characterized by comprising the following specific steps:
(1) drying, crushing and grinding the diamond wire cutting silicon waste to obtain waste silicon powder, soaking and purifying the waste silicon powder in an alkali-alcohol solution under the stirring condition, carrying out solid-liquid separation, and washing the solid with deionized water until the washing liquid is neutral to obtain purified silicon powder;
(2) placing the purified silicon powder obtained in the step (1) in an HF-metal salt-alcohol solution system for metal-assisted etching treatment, ultrasonically rinsing by using deionized water, carrying out solid-liquid separation, drying the solid in vacuum, and grinding to obtain a nano metal/porous silicon composite material;
(3) uniformly mixing the nano metal/porous silicon composite material obtained in the step (2) with a boron source to obtain a mixture, and treating the mixture at the constant temperature of 400-1200 ℃ in a protective atmosphere for 0.5-12h to obtain a boron-doped nano metal/porous silicon composite material;
(4) soaking the boron-doped nano metal/porous silicon composite material obtained in the step (3) in an alkali solution, performing solid-liquid separation, performing vacuum drying on the solid, and grinding to obtain a high-purity boron-doped nano metal/porous silicon composite material;
(5) and (4) uniformly mixing the high-purity boron-doped nano metal/porous silicon composite material obtained in the step (4) with a carbon material to obtain the boron-doped nano metal/porous silicon-carbon composite cathode.
2. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the mass concentration of alkali in the alkali-alcohol solution is 1-30%, and the alkali is NaOH, KOH or Ba (OH)2、Ca(OH)2One or more alcohols selected from methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the soaking and purifying treatment time is 1-300 min.
3. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the concentration of HF, the concentration of metal salt and the concentration of alcohols in the HF-metal salt-alcohol solution system are respectively 0.1-20 mol/L, 0.05-5 mol/L and 0.1-20 mol/L; the metal salt is one or more of silver salt, copper salt and nickel salt, the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol, and the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the purified silicon powder is (10-100) to 1.
4. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 3, wherein the method comprises the following steps: the silver salt in the step (2) is AgNO3、Ag2SO4Or Ag2CO3Copper salt being Cu (NO)3)2、CuSO4Or CuCO3The nickel salt is Ni (NO)3)2、NiSO4Or NiCO3。
5. The method for preparing a boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste materials according to claim 1 or 3, characterized in that: in the step (2), the temperature of the metal auxiliary etching treatment is 1-100 ℃, and the time of the metal auxiliary etching treatment is 1-600 min.
6. The method for preparing a boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste according to claim 1 or 2, characterized in that: and (3) the boron source is one or more of boric acid, boron oxide, boron nitride, trimethyl borate, tripropyl borate, boron tribromide and diborane, and the protective atmosphere is argon or nitrogen.
7. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the alkali solution in the step (4) is KOH solution, Ba (OH)2Solution, NaOH solution, Ca (OH)2One or more of the solutions.
8. The method for preparing a boron-doped nano-metal/porous silicon-carbon composite anode based on cutting silicon waste materials according to claim 1 or 7, characterized in that: the concentration of the aqueous alkali in the step (4) is 0.1-10 mol/L, the soaking temperature is 1-100 ℃, and the soaking time is 1-120 min.
9. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the mass fraction of boron in the high-purity boron-doped nano metal/porous silicon composite material is 1-20%.
10. The method for preparing the boron-doped nano metal/porous silicon-carbon composite anode based on cutting the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the carbon material is one or more of graphite, carbon nano tubes, graphene and pyrolytic carbon, the pyrolytic carbon is carbon formed by pyrolysis of one or more of polydopamine, resorcinol-formaldehyde resin, polyvinylpyrrolidone, saccharide materials and aromatic compounds, and the mass fraction of the carbon material in the boron-doped nano metal/porous silicon carbon composite negative electrode is 1-50%.
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| CN112259719A (en) * | 2020-10-22 | 2021-01-22 | 昆明理工大学 | Comprehensive recovery method of waste photovoltaic module and preparation method of silicon-carbon negative electrode material |
| CN113732013A (en) * | 2021-08-27 | 2021-12-03 | 昆明理工大学 | Microwave catalytic treatment method for waste photovoltaic module and silicon-carbon composite material obtained by microwave catalytic treatment method |
| CN113851619A (en) * | 2021-08-20 | 2021-12-28 | 武汉科技大学 | Method for preparing silicon-carbon composite negative electrode material for lithium ion battery by using metallurgical waste silicon powder |
| CN115732649A (en) * | 2022-08-15 | 2023-03-03 | 湖北亿纬动力有限公司 | B-doped silicon monoxide negative electrode material and preparation method and application thereof |
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