CN111785944A - Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activation cutting of silicon waste - Google Patents
Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activation cutting of silicon waste Download PDFInfo
- Publication number
- CN111785944A CN111785944A CN202010699399.2A CN202010699399A CN111785944A CN 111785944 A CN111785944 A CN 111785944A CN 202010699399 A CN202010699399 A CN 202010699399A CN 111785944 A CN111785944 A CN 111785944A
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- nano
- waste
- nano metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 118
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 97
- 239000010703 silicon Substances 0.000 title claims abstract description 97
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000005520 cutting process Methods 0.000 title claims abstract description 42
- 239000002905 metal composite material Substances 0.000 title claims abstract description 39
- 238000000678 plasma activation Methods 0.000 title claims abstract description 33
- 239000010405 anode material Substances 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 100
- 239000002923 metal particle Substances 0.000 claims abstract description 35
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 28
- 238000009833 condensation Methods 0.000 claims abstract description 19
- 230000005494 condensation Effects 0.000 claims abstract description 19
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 17
- 239000010432 diamond Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 238000002309 gasification Methods 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 76
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 239000011812 mixed powder Substances 0.000 claims description 51
- 239000011863 silicon-based powder Substances 0.000 claims description 41
- 229910052786 argon Inorganic materials 0.000 claims description 38
- 238000001291 vacuum drying Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 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
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 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 claims description 2
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 239000003245 coal Substances 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
- 239000008103 glucose Substances 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
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000009830 intercalation Methods 0.000 abstract description 9
- 230000002687 intercalation Effects 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract description 9
- 239000000843 powder Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000007709 nanocrystallization Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 9
- 239000002114 nanocomposite Substances 0.000 description 9
- 230000001476 alcoholic effect Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 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
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation, and belongs to the technical field of new energy materials and electrochemistry. The method comprises the steps of uniformly mixing diamond wire cutting silicon waste with carbon source powder, carrying out plasma activation treatment, carrying out gasification, condensation and recrystallization on silicon and carbon to obtain a nano silicon/carbon composite material, removing impurities in the silicon waste and realizing nanocrystallization of silicon and carbon through the plasma activation treatment, and carrying out nano metal particle compounding on the silicon/carbon composite material to prepare the porous silicon/carbon/nano metal composite material. The porous silicon/carbon/nano metal composite negative electrode material prepared by the invention can shorten the transmission distance of lithium ions and electrons, improve the integral conductivity and structural integrity of the electrode material, and effectively solve the problems of huge volume change and low rate capability in the lithium desorption and intercalation process.
Description
Technical Field
The invention relates to a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation, and belongs to the technical field of new energy materials and electrochemistry.
Background
In the structure of the lithium ion battery, the important components of the negative electrode material directly determine the quality and application of the lithium ion battery. Hitherto, the negative electrode material of lithium ion batteries mainly includes carbon materials, lithium alloys (lithium silicon alloys, lithium tin alloys, etc.), transition metal oxides (TiO)2、SnO2Etc.), nitrides. The graphite material has good cycle stability, excellent conductivity and good lithium intercalation space in the layered structure, and the volume change is within an acceptable range in the lithium intercalation and deintercalation process, so the graphite negative electrode material is applied to the lithium battery industryIs widely applied. However, with the rapid development of electronic technology and the rapid popularization of electric vehicles, the market demand for high specific capacity lithium ion batteries is becoming stronger. However, the theoretical specific discharge capacity of the graphite cathode material which is commercialized at present is only 372mAh/g, and the actual capacity of the graphite cathode material which is put into production is very close to this, so that the demand of the power type lithium ion battery for high-energy storage equipment in the fields of electric automobiles and electronic industry is difficult to meet. Therefore, the development of a lithium ion battery cathode material with high specific discharge capacity has been an urgent problem to be solved.
The Si negative electrode material has higher theoretical specific capacity which can reach 4200mAh/g at most, has the advantages of a low-voltage platform, low reactivity with electrolyte, rich reserve in crust, low price and the like, is a lithium battery negative electrode material with great prospect, but has fatal defects, namely the problems of huge volume change and low intrinsic conductivity in the charging and discharging process. Volume expansion is a problem that any lithium ion electrode material faces during both delithiation and intercalation, but this problem is particularly acute with Si cathodes. Under the state of complete lithium intercalation, the volume expansion of the Si negative electrode can reach 300 percent, which not only can cause the Si negative electrode to generate cracks and even be broken, but also can damage the structure of a negative electrode piece, cause the irreversible loss of the battery capacity and simultaneously generate potential safety hazards. In addition, the intrinsic semiconductor properties of silicon are also a non-negligible problem. Because the intrinsic conductivity of Si is very low, the rate performance of the battery is severely limited, and the practical application value of the battery is directly influenced.
In recent years, most of domestic and foreign production enterprises widely adopt diamond wire cutting technology to process silicon wafers in the process of silicon wafer production. In the process of cutting the solar silicon wafer on line, due to collision and friction between the linear cutting tool and the silicon wafer, besides generated broken silicon particles, the tool can be partially broken and worn, lubricating liquid and cooling liquid in the cutting process can be mixed into a cutting system to form cut silicon waste, about 40% of high-purity silicon can be wasted, and only in 2019 years, for example, when the 132GW silicon wafer is cut, up to 30 ten thousand tons of cut waste can be generated. However, effective recovery of high-purity silicon powder in the waste materials is difficult to realize according to the existing recovery methods such as flotation, cyclone separation and the like, and the silicon is seriously polluted in the cutting process and cannot be directly used in photovoltaic and electronic industries.
Disclosure of Invention
Aiming at the problems that the lithium battery silicon cathode in the prior art is high in cost, huge volume change and low in intrinsic conductivity in the silicon material circulation process are caused, and diamond wire cutting silicon waste in the photovoltaic industry is difficult to recycle, the invention provides a method for preparing a porous silicon/carbon/nano metal composite cathode material by plasma activation cutting silicon waste. According to the invention, the high-performance cathode material of the lithium ion battery, namely the porous silicon/carbon/nano metal composite cathode, is prepared from the cut silicon waste by adopting a plasma activation composite-nano metal particle composite combined treatment method, so that the transmission distance of lithium ions and electrons can be shortened, the integral conductivity and structural integrity of the electrode material are improved, and the problems of huge volume change and low rate capability in the lithium desorption and intercalation process are effectively solved.
The method for preparing the porous silicon/carbon/nano metal composite anode material by cutting the silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the diamond wire cutting silicon waste to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder obtained in the step (1) with a carbon source, and performing vacuum drying to obtain silicon-carbon mixed powder;
(3) introducing argon into the plasma furnace to remove air in the furnace body, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace to perform plasma activation treatment by taking the argon as protective gas and carrier gas, and performing gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material);
(4) and (3) placing the Nano silicon/carbon composite material in the step (3) in an HF-metal salt-alcohol solution system for metal particle Nano particle compounding, washing with deionized water, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-M composite material).
And (3) the mass fraction of the waste silicon powder in the silicon-carbon mixed powder in the step (2) is 3-100%. The waste silicon powder and the carbon source are mixed by manual mixing, mechanical stirring, ball milling mixing or high-energy ball milling mixing;
the carbon source in the step (2) is one or more of glucose, fructose, sucrose, xylose, sorbose, citric acid, starch, polyethylene, polypropylene, cellulose, graphite, graphene, carbon nano tubes, aromatic hydrocarbon, aromatic lipid, petroleum asphalt or coal asphalt.
The power of the plasma activation treatment in the step (3) is 10-150 KW, the argon pressure is 0.10-0.70 Mpa, and the feeding rate of the silicon-carbon mixed powder is 1-50 g/min.
The silicon-carbon mixed powder is gasified, condensed and recrystallized to enable carbon to be compounded on the surface of the silicon to obtain a nano silicon/carbon composite material, the structure of the nano silicon/carbon composite material is a nano silicon structure coated by graphene and/or a nano silicon structure compounded by carbon nano tubes, the particle size of the nano silicon/carbon composite material is controllable, and the particle size is 10-150 nm;
in the step (4), the concentration of HF, the concentration of metal salt and the concentration of alcohols in the HF-metal salt-alcohol solution system are respectively 0.1-15 mol/L, 0.005-10 mol/L and 0.1-20 mol/L;
further, the metal salt is one or more of silver salt, copper salt, cobalt salt, nickel salt, aluminum salt and titanium salt, and the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
Preferably, the silver salt is AgNO3、Ag2SO4Or Ag2CO3Copper salt being Cu (NO)3)2、CuSO4Or CuCO3The nickel salt is Ni (NO)3)2、NiSO4Or NiCO3The cobalt salt being Co (NO)3)2The aluminum salt is Al (NO)3)3。
The liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the nano silicon/carbon composite material is (1-10): 1.
The composite temperature of the metal particle nano-particles is 20-80 ℃, and the time is 0.5-6 h.
The invention has the beneficial effects that:
(1) the nano-size and the porous structure of the porous silicon/carbon/nano-metal composite material can effectively remove the huge volume change in the lithium intercalation process, simultaneously shorten the transmission distance of lithium ions and electrons, effectively overcome the problem of low conductivity of a silicon material after the metal particles are compounded with the porous silicon, improve the overall conductivity of an electrode material, and improve the stability of the overall structure of the material and enhance the overall conductivity of the material again due to the introduction of carbon;
(2) according to the invention, waste silicon powder is prepared into a nanometer grade by a plasma activation process so as to solve the problems of poor silicon intrinsic conductivity and huge volume expansion in the lithium intercalation and deintercalation process, carbon and metal ions effectively improve the problem of low silicon intrinsic conductivity, and the nanometer grade of the porous silicon/carbon/nanometer metal composite material can ensure the structural integrity of an electrode material in charge and discharge cycles, so that the cycle stability of the electrode is improved, and the nanometer size effect can effectively accelerate the phase transformation of an active substance and reduce the absolute volume effect of the active substance in the lithium intercalation and deintercalation process and the diffusion distance of lithium ions in the material;
(3) the method for preparing the porous silicon/carbon/nano metal composite cathode by taking photovoltaic linear cutting silicon waste as the raw material has simple process, is suitable for industrial production, greatly saves the raw material cost, improves the resource utilization rate and realizes changing waste into valuable.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of virgin diamond wire-cut silicon scrap of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the pSi/C/Nano-Ag composite material of example 1;
fig. 3 is a cycle performance curve at a rate of 0.5C after the original silicon scrap and the porous silicon/carbon/nano silver composite material are assembled into a half cell in example 1.
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 porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 50%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 110A, the voltage is 140V, the argon pressure is 0.2MPa, the feeding rate of the silicon-carbon mixed powder is 1g/min, and organic impurities in the waste silicon powder can be directly taken out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material in the step (3) in HF-AgNO3-compounding metal particle nanoparticles in an alcoholic solution system at a temperature of 80 ℃ for 4h, wherein HF-AgNO3HF concentration in the ethanol solution system of 0.5mol/L, AgNO3The concentration is 0.1mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano silver composite material (PSi/C/Nano-Ag composite material);
a Scanning Electron Microscope (SEM) image of an original diamond wire-cut silicon waste is shown in fig. 1, and it can be seen from fig. 1 that particles of the original diamond wire-cut silicon waste are not uniform in size and have huge difference, if the original diamond wire-cut silicon waste is directly applied to a lithium ion battery cathode, a cathode can generate huge volume change in a lithium desorption process in a discharge process, so that capacity is rapidly attenuated, and the lithium ion battery of the cathode is rapidly disabled in a circulation process due to damage of the cathode;
a Scanning Electron Microscope (SEM) image of the pSi/C/Nano-Ag composite material is shown in fig. 2, and it can be seen from fig. 2 that the Nano silver particles are uniformly distributed on the surface of the porous silicon particles, the porous silicon/carbon/Nano metal composite negative electrode material has a porous structure formed by stacking porous Nano spheres, and a large number of porous structures exist in the spheres and between the spheres; the diffusion speed of lithium ions in the negative electrode material is greatly increased, and meanwhile, a large amount of space is reserved for volume expansion caused by lithium desorption in the charge and discharge process by the porous structure in the sphere, so that the volume expansion is greatly relieved;
the cycle performance curve of the original silicon waste and the porous silicon/carbon/nano silver composite material assembled into the half-cell at the multiplying power of 0.5C is shown in figure 3, the initial capacity of the original silicon waste cathode is 2970mAh/g, but after 20 cycles, the capacity is less than 500mAh/g, the capacity attenuation is extremely fast, and meanwhile, the initial coulombic efficiency is only 58%; the initial capacity of the porous silicon/carbon/nano silver composite negative electrode is 2788mAh/g, the initial capacity is only slightly lower than that of the original silicon waste negative electrode, after 50 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite negative electrode material is basically stabilized at 1250mAh/g, and lithium ion transmission can be greatly improved due to nano silver ions in the porous silicon/carbon/nano silver composite negative electrode.
Example 2: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 18 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 60%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 1.5g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material obtained in the step (3) in HF-Cu (NO)3)2-compounding of metal particles nanoparticles in an alcoholic solution system and at a temperature of 40 ℃ for 6h, wherein HF-Cu (NO)3)2HF concentration in the ethanol solution system 0.5mol/L, Cu (NO)3)2The concentration is 0.2mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Cu composite material); the composite material is prepared into a silicon cathode half cell, and after 50 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1200 mAh/g.
Example 3: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 3 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 60%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material in the step (3) in HF-Ni (NO)3)2-compounding of metal particle nanoparticles in an alcoholic solution system at a temperature of 80 ℃ for 2h, wherein HF-Ni (NO)3)2HF concentration in the ethanol solution system 0.5mol/L, Ni (NO)3)2The concentration is 0.2mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ni composite material); the composite material is prepared into a silicon cathode half cell, and after 60 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1100 mAh/g.
Example 4: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 5 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 16 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 80%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 120A, the voltage is 130V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material obtained in the step (3) in HF-Co (NO)3)2-compounding of metal particle nanoparticles in an alcoholic solution system at a temperature of 60 ℃ for 3h, wherein HF-Co (NO)3)2HF concentration in the ethanol solution system 0.5mol/L, Co (NO)3)2The concentration is 0.2mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Co composite material); the composite material is prepared into a silicon cathode half cell, and after 50 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1180 mAh/g.
Example 5: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 6 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 12 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 90%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 110A, the voltage is 140V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material obtained in the step (3) in HF-Al (NO)3)3-compounding of metal particles nanoparticles in an alcoholic solution system at a temperature of 60 ℃ for 3h, wherein HF-Al (NO)3)3HF concentration in the ethanol solution system 0.5mol/L, Al (NO)3)3The concentration is 0.15mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Al composite material); the composite material is prepared into a silicon cathode half cell, and after 40 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1150 mAh/g.
Example 6: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 90%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 110A, the voltage is 140V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material in the step (3) in HF-AgNO3-Cu(NO3)2-carrying out the metal particle nano-sizing in an alcoholic solution system at a temperature of 80 DEG CCompounding rice particles for 4h, wherein the HF-AgNO3-Cu(NO3)2HF concentration in the ethanol solution system of 0.5mol/L, AgNO3The concentration was 0.10mol/L, Cu (NO)3)2The concentration is 0.05mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ag @ Cu composite material); the composite material is prepared into a silicon cathode half cell, and after 50 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1100 mAh/g.
Example 7: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 80%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 110A, the voltage is 140V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material in the step (3) in HF-AgNO3-Co(NO3)2-compounding metal particle nanoparticles in an alcoholic solution system at a temperature of 80 ℃ for 4h, wherein HF-AgNO3-Co(NO3)2HF in ethanol solution systemThe concentration is 0.5mol/L, AgNO3The concentration was 0.10mol/L, Co (NO)3)2The concentration is 0.10mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Ag @ Co composite material); the composite material is prepared into a silicon cathode half cell, and after 40 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1150 mAh/g.
Example 8: a method for preparing a porous silicon/carbon/nano metal composite anode material by cutting silicon waste through plasma activation comprises the following specific steps:
(1) crushing, grinding and vacuum drying the photovoltaic diamond wire cutting silicon waste for 4 hours to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder and the carbon source obtained in the step (1) in a high-energy ball mill through ball milling, sieving with a 300-mesh sieve, and performing vacuum drying for 24 hours to obtain silicon-carbon mixed powder, wherein the mass fraction of the waste silicon powder in the silicon-carbon mixed powder is 70%;
(3) introducing pure argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace through a powder inlet device to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain a nano silicon/carbon composite material (PSi/C nano composite material); wherein the current of the plasma furnace is 110A, the voltage is 140V, the argon pressure is 0.15MPa, the feeding rate of the silicon-carbon mixed powder is 2.0g/min, and organic impurities in the waste silicon powder can be directly brought out by argon in a gas form due to the extremely low condensation temperature relative to silicon-carbon to realize the purification of silicon;
(4) placing the nano silicon/carbon composite material obtained in the step (3) in HF-Co (NO)3)2-Cu(NO3)2-Ni(NO3)2-compounding of metal particle nanoparticles in an alcoholic solution system at a temperature of 80 ℃ for 4h, wherein HF-Co (NO)3)2-Cu(NO3)2-Ni(NO3)2HF concentration of 0 in the ethanol solution system.5mol/L、Co(NO3)2The concentration is 0.06mol/L, Cu (NO)3)2The concentration was 0.10mol/L, Ni (NO)3)2The concentration is 0.04mol/L, and the ethanol concentration is 0.5 mol/L; ultrasonically rinsing with deionized water until the washing liquid is neutral, performing solid-liquid separation to obtain a Nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the Nano metal particle composite silicon/carbon composite material to obtain a porous silicon/carbon/Nano metal composite material (PSi/C/Nano-Co @ Cu @ Ni composite material); the composite material is prepared into a silicon cathode half cell, and after 60 times of charge-discharge cycles, the capacity of the porous silicon/carbon/nano silver composite cathode material is basically stabilized at 1200 mAh/g.
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 (9)
1. The method for preparing the porous silicon/carbon/nano metal composite anode material by cutting the silicon waste through plasma activation is characterized by comprising the following specific steps of:
(1) crushing, grinding and vacuum drying the diamond wire cutting silicon waste to obtain waste silicon powder;
(2) uniformly mixing the waste silicon powder obtained in the step (1) with a carbon source, and performing vacuum drying to obtain silicon-carbon mixed powder;
(3) introducing argon into the plasma furnace to remove air in the furnace body, taking the argon as protective gas and carrier gas, introducing the silicon-carbon mixed powder obtained in the step (2) into the plasma furnace to carry out plasma activation treatment, and carrying out gasification condensation and recrystallization on the silicon-carbon mixed powder to obtain the nano silicon/carbon composite material;
(4) and (3) placing the nano silicon/carbon composite material in the step (3) in an HF-metal salt-alcohol solution system for metal particle nano particle compounding, washing with deionized water, performing solid-liquid separation to obtain a nano metal particle composite silicon/carbon composite material, and performing vacuum drying treatment and grinding on the nano metal particle composite silicon/carbon composite material to obtain the porous silicon/carbon/nano metal composite material.
2. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activated cutting of the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: and (3) the mass fraction of the waste silicon powder in the silicon-carbon mixed powder in the step (2) is 3-100%.
3. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activated cutting of the silicon waste material according to claim 1 or 2, characterized in that: the carbon source in the step (2) is one or more of glucose, fructose, sucrose, xylose, sorbose, citric acid, starch, polyethylene, polypropylene, cellulose, graphite, graphene, carbon nano tubes, aromatic hydrocarbon, aromatic lipid, petroleum asphalt or coal asphalt.
4. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activated cutting of the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: the power of the plasma activation treatment in the step (3) is 10-150 KW, the argon pressure is 0.10-0.70 MPa, and the feeding rate of the silicon-carbon mixed powder is 1-50 g/min.
5. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activated cutting of the silicon waste material as claimed in claim 1, wherein the method comprises the following steps: in the step (4), the concentration of HF, the concentration of metal salt and the concentration of alcohol in the HF-metal salt-alcohol solution system are respectively 0.1-15 mol/L, 0.005-10 mol/L and 0.1-20 mol/L.
6. The method for preparing the porous silicon/carbon/nano metal composite anode material by plasma activated cutting of the silicon waste material as claimed in claim 5, wherein the method comprises the following steps: the metal salt is one or more of silver salt, copper salt, cobalt salt, nickel salt, aluminum salt and titanium salt, and the alcohol is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, allyl alcohol and vinyl alcohol.
7. The method for preparing porous silicon/carbon/nano-metal composite negative by plasma activated cutting of silicon waste material according to claim 6A method of pole material, characterized by: the silver salt being AgNO3、Ag2SO4Or Ag2CO3Copper salt being Cu (NO)3)2、CuSO4Or CuCO3The nickel salt is Ni (NO)3)2、NiSO4Or NiCO3The cobalt salt being Co (NO)3)2The aluminum salt is Al (NO)3)3。
8. The method for preparing the porous silicon/carbon/nano metal composite anode material by cutting the silicon waste through plasma activation according to claim 1 or 5, is characterized in that: the liquid-solid ratio mL of the HF-metal salt-alcohol solution system to the nano silicon/carbon composite material is (1-10): 1.
9. The method for preparing the porous silicon/carbon/nano metal composite anode material by cutting the silicon waste through plasma activation according to claim 1 or 5, is characterized in that: the compounding temperature of the metal particle nano-particles is 20-80 ℃, and the time is 0.5-6 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010699399.2A CN111785944B (en) | 2020-07-20 | 2020-07-20 | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010699399.2A CN111785944B (en) | 2020-07-20 | 2020-07-20 | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111785944A true CN111785944A (en) | 2020-10-16 |
| CN111785944B CN111785944B (en) | 2023-04-28 |
Family
ID=72764338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010699399.2A Active CN111785944B (en) | 2020-07-20 | 2020-07-20 | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111785944B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112467067A (en) * | 2020-12-02 | 2021-03-09 | 郑州中科新兴产业技术研究院 | Three-dimensional porous silicon-carbon material prepared by purifying photovoltaic silicon mud and preparation method thereof |
| WO2024000823A1 (en) * | 2022-06-29 | 2024-01-04 | 溧阳天目先导电池材料科技有限公司 | Multi-hierarchical composite material prepared at ultra-high temperature, and preparation method therefor and use thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101390198A (en) * | 2006-01-23 | 2009-03-18 | 奈克松有限公司 | Method of etching a silicon-based material |
| CN102403491A (en) * | 2011-11-30 | 2012-04-04 | 奇瑞汽车股份有限公司 | Silicon carbon composite anode material of lithium-ion battery, method for preparing silicon carbon composite anode material, and lithium-ion battery |
| KR101396846B1 (en) * | 2013-07-09 | 2014-05-19 | 한국에너지기술연구원 | Method of manufacturing anode materials for lithium secondary battery using waste silicon |
| CN108793169A (en) * | 2017-03-27 | 2018-11-13 | 储晞 | A kind of square law device and system recycling Buddha's warrior attendant wire cutting silicon material by-product silicon mud |
| CN108899521A (en) * | 2018-07-09 | 2018-11-27 | 西北大学 | Utilize waste silicon powder and the compound method for preparing ion cathode material lithium of carbon |
| CN109904407A (en) * | 2019-01-02 | 2019-06-18 | 昆明理工大学 | A kind of method that Buddha's warrior attendant wire cutting scrap silicon prepares lithium ion battery negative material |
| CN110289408A (en) * | 2019-06-26 | 2019-09-27 | 东北大学 | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon |
| CN110350181A (en) * | 2019-07-16 | 2019-10-18 | 昆明理工大学 | A kind of preparation method of lithium ion cell nano porous silicon negative electrode material |
-
2020
- 2020-07-20 CN CN202010699399.2A patent/CN111785944B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101390198A (en) * | 2006-01-23 | 2009-03-18 | 奈克松有限公司 | Method of etching a silicon-based material |
| CN102403491A (en) * | 2011-11-30 | 2012-04-04 | 奇瑞汽车股份有限公司 | Silicon carbon composite anode material of lithium-ion battery, method for preparing silicon carbon composite anode material, and lithium-ion battery |
| KR101396846B1 (en) * | 2013-07-09 | 2014-05-19 | 한국에너지기술연구원 | Method of manufacturing anode materials for lithium secondary battery using waste silicon |
| CN108793169A (en) * | 2017-03-27 | 2018-11-13 | 储晞 | A kind of square law device and system recycling Buddha's warrior attendant wire cutting silicon material by-product silicon mud |
| CN108899521A (en) * | 2018-07-09 | 2018-11-27 | 西北大学 | Utilize waste silicon powder and the compound method for preparing ion cathode material lithium of carbon |
| CN109904407A (en) * | 2019-01-02 | 2019-06-18 | 昆明理工大学 | A kind of method that Buddha's warrior attendant wire cutting scrap silicon prepares lithium ion battery negative material |
| CN110289408A (en) * | 2019-06-26 | 2019-09-27 | 东北大学 | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon |
| CN110350181A (en) * | 2019-07-16 | 2019-10-18 | 昆明理工大学 | A kind of preparation method of lithium ion cell nano porous silicon negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 范亚昆: "热等离子体法制备球形纳米硅粉", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112259719B (en) * | 2020-10-22 | 2022-09-16 | 昆明理工大学 | Comprehensive recovery method of waste photovoltaic module and preparation method of silicon-carbon negative electrode material |
| CN112467067A (en) * | 2020-12-02 | 2021-03-09 | 郑州中科新兴产业技术研究院 | Three-dimensional porous silicon-carbon material prepared by purifying photovoltaic silicon mud and preparation method thereof |
| CN112467067B (en) * | 2020-12-02 | 2021-10-29 | 郑州中科新兴产业技术研究院 | Three-dimensional porous silicon-carbon material prepared by purifying photovoltaic silicon mud and preparation method thereof |
| WO2024000823A1 (en) * | 2022-06-29 | 2024-01-04 | 溧阳天目先导电池材料科技有限公司 | Multi-hierarchical composite material prepared at ultra-high temperature, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111785944B (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111326723B (en) | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| WO2020140602A1 (en) | Porous silicon material and preparation method therefor, negative battery material, and electrochemical battery | |
| CN110767877B (en) | Lithium ion battery silicon monoxide negative electrode material and preparation method and application thereof | |
| CN112366301B (en) | Silicon/silicon oxide/carbon composite negative electrode material for lithium ion battery and preparation method thereof | |
| Xi et al. | PSi@ SiOx/Nano-Ag composite derived from silicon cutting waste as high-performance anode material for Li-ion batteries | |
| Wei et al. | Review of room-temperature liquid metals for advanced metal anodes in rechargeable batteries | |
| CN111785944B (en) | Method for preparing porous silicon/carbon/nano metal composite anode material by plasma activated cutting silicon waste | |
| CN108390053B (en) | Sheet boron-doped porous silicon electrode material and preparation method thereof | |
| CN104638253B (en) | A kind of preparation method of the Si@C RG composite material of core-shell structure as lithium ion battery negative | |
| CN110474032A (en) | It is a kind of to be given up the silicon-carbon cathode material and preparation method thereof of silicon based on photovoltaic | |
| CN111048757B (en) | B. N-codoped graphene-coated silicon nano anode material and preparation method thereof | |
| CN111252757A (en) | Method for preparing graphene by using waste lithium ion power battery | |
| CN111653734A (en) | Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof | |
| CN104862514A (en) | Surface modifying method of AB3 type hydrogen storage alloy | |
| EP4273966A1 (en) | Silicon-doped graphene composite material, preparation method for same, and applications thereof | |
| CN109360942B (en) | Method for preparing lithium ion battery cathode based on recycled solar battery | |
| CN102887504A (en) | Method for preparing carbon material for lithium ion battery cathode | |
| Wang et al. | High-performance anode of lithium ion batteries with plasma-prepared silicon nanoparticles and a three-component binder | |
| CN109148868B (en) | Flaky silicon particles for negative electrode of lithium battery | |
| CN105406041A (en) | Hollow titanium oxide composite material, and preparation method and application thereof | |
| CN113428865B (en) | Pomegranate-like silicon-based negative electrode material and preparation method thereof | |
| CN115275154A (en) | Method for preparing high-performance silicon-carbon negative electrode from natural graphite spherical tailings | |
| CN114927675A (en) | Composite metal-coated silicon carbide-based negative electrode material and preparation method and application thereof | |
| CN114079044B (en) | Three-dimensional porous silicon/graphene composite anode material, preparation method thereof and lithium ion battery | |
| CN110752357B (en) | Porous Fe-based amorphous alloy coated silicon cathode of lithium battery and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |