CN104617278A - Nano silicon metal composite material and preparation method thereof - Google Patents
Nano silicon metal composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104617278A CN104617278A CN201310538238.5A CN201310538238A CN104617278A CN 104617278 A CN104617278 A CN 104617278A CN 201310538238 A CN201310538238 A CN 201310538238A CN 104617278 A CN104617278 A CN 104617278A
- Authority
- CN
- China
- Prior art keywords
- silicon
- metal
- nano
- composite material
- metal composite
- 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 92
- 239000002905 metal composite material Substances 0.000 title claims abstract description 77
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 236
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 claims abstract description 90
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 89
- 239000002184 metal Substances 0.000 claims abstract description 85
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 80
- 239000010703 silicon Substances 0.000 claims abstract description 78
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 83
- 239000000203 mixture Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 38
- 239000000084 colloidal system Substances 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 239000008119 colloidal silica Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims 2
- 229940075614 colloidal silicon dioxide Drugs 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 235000011148 calcium chloride Nutrition 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- 229910052681 coesite Inorganic materials 0.000 description 38
- 229910052906 cristobalite Inorganic materials 0.000 description 38
- 229910052682 stishovite Inorganic materials 0.000 description 38
- 229910052905 tridymite Inorganic materials 0.000 description 38
- 239000000843 powder Substances 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 230000004927 fusion Effects 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 238000011056 performance test Methods 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 238000009830 intercalation Methods 0.000 description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 230000002687 intercalation Effects 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- 229910000480 nickel oxide Inorganic materials 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002070 nanowire Substances 0.000 description 6
- 229910021332 silicide Inorganic materials 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229910005881 NiSi 2 Inorganic materials 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- -1 silicon oxide compound Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910008484 TiSi Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910005329 FeSi 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 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 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229920002472 Starch 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KMTYGNUPYSXKGJ-UHFFFAOYSA-N [Si+4].[Si+4].[Ni++] Chemical compound [Si+4].[Si+4].[Ni++] KMTYGNUPYSXKGJ-UHFFFAOYSA-N 0.000 description 1
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910021334 nickel silicide Inorganic materials 0.000 description 1
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011869 silicon-nickel composite material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- H01M4/38—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
一种用于锂离子电池负极的纳米硅金属复合材料。该锂离子电池用纳米硅金属复合材料是由下述组成部分和含量所组成的：(a)第一组成部分为单质硅，其含量相对于纳米硅金属复合材料为5～75mol％；(b)第二组成部分包含金属元素、金属元素与硅形成的化合物和硅氧化合物，第二组成部分的含量相对于纳米硅复合材料为25～95mol％；(c)第三组成部分为单质碳，其含量相对于纳米硅金属复合材料为0～70mol％。其制备方法是以二氧化硅与金属或金属氧化物等组成的多孔块体与导电的阴极集流体复合作为阴极，以石墨或惰性阳极作为阳极，置于以CaCl2或以CaCl2为主的混盐熔体电解质中，在阴极和阳极之间施加电压，控制电流密度和电解电量，使得多孔块体中的二氧化硅电解还原成纳米硅，在阴极制得纳米硅金属复合材料。
A nano-silicon-metal composite material used for the negative electrode of lithium-ion batteries. The nano-silicon-metal composite material for lithium-ion batteries is composed of the following components and content: (a) the first component is elemental silicon, and its content is 5 to 75 mol% relative to the nano-silicon-metal composite material; (b) ) The second component includes metal elements, compounds formed by metal elements and silicon, and silicon-oxygen compounds, and the content of the second component is 25 to 95 mol% relative to the nano-silicon composite material; (c) the third component is elemental carbon, Its content is 0-70 mol% relative to the nano-silicon-metal composite material. Its preparation method is to combine a porous block composed of silicon dioxide and metal or metal oxide with a conductive cathode current collector as the cathode, use graphite or an inert anode as the anode, and place it in a CaCl2 or CaCl2- based In the mixed salt melt electrolyte, a voltage is applied between the cathode and the anode to control the current density and electrolysis power, so that the silicon dioxide in the porous block is electrolytically reduced to nano-silicon, and the nano-silicon-metal composite material is prepared at the cathode.
Description
技术领域technical field
本发明涉及一种锂离子电池用硅金属复合材料及其制备方法。The invention relates to a silicon-metal composite material for a lithium ion battery and a preparation method thereof.
背景技术Background technique
锂离子二次电池在各种电子设备中广泛应用。随着电子设备的发展对其动力系统-化学电源的需求和性能的要求急剧增长，大多数商业化锂离子电池具有包含如石墨材料的阳极，该材料在充电时通过插入机理引入锂。这种插入型阳极表现出较好的循环寿命和库伦效率，但是受限于较低的理论容量(372mAh／g)很难通过电池制备工艺来提高电池的性能。Lithium-ion secondary batteries are widely used in various electronic devices. With the development of electronic devices, the demand and performance requirements of their power systems - chemical power sources - have increased dramatically. Most commercial Li-ion batteries have anodes containing materials such as graphite, which incorporate lithium through an intercalation mechanism during charging. This insertion type anode shows good cycle life and coulombic efficiency, but limited by the low theoretical capacity (372mAh/g), it is difficult to improve the performance of the battery through the battery preparation process.
Si、Sn和Sb等第二类阳极材料，其在充电时通过合金化机理引入锂，是高容量阳极材料的较好选择，其中硅具有比广泛使用的碳材料10倍多得理论电化学容量(4200mAh／g)，低的嵌锂电压(低于0.5V)，嵌入过程不存在溶剂分子的共嵌入，在地壳中含量丰富等优点。但是硅材料做为阳极表现出相对较差的循环寿命和库伦效率，主要原因是硅材料本身导电性能差，并且在电化学脱嵌锂过程产生的严重体积效应(体积变化率：280％～310％)，产生的内应力造成了材料结构的破坏，导致电极材料间、电极材料与导电剂(如碳)和粘合剂、电极材料与集流体的分离，进而失去电接触，导致电极的循环性能加速下降。The second class of anode materials, Si, Sn, and Sb, which introduce lithium through an alloying mechanism during charging, is a better choice for high-capacity anode materials, where silicon has a theoretical electrochemical capacity 10 times greater than that of widely used carbon materials (4200mAh/g), low lithium intercalation voltage (less than 0.5V), no co-intercalation of solvent molecules in the intercalation process, and rich content in the earth's crust. However, silicon materials show relatively poor cycle life and coulombic efficiency as anodes, mainly due to the poor electrical conductivity of silicon materials and the serious volume effect (volume change rate: 280% to 310 %), the generated internal stress caused the destruction of the material structure, leading to the separation between the electrode materials, the electrode material and the conductive agent (such as carbon) and the binder, the electrode material and the current collector, and then lost the electrical contact, resulting in the cycle of the electrode Performance degrades at an accelerated rate.
目前人们提出解决这一问题的办法主要有两种：方法之一就是将硅纳米化。因为随着颗粒的减小，在一定程度上能够降低硅的体积变化，减小电极内部应力。但纳米材料在循环过程中易团聚，不足以使电池的性能改善到实用化。第二，采用硅与金属等材料复合，即将具有电化学活性的纳米硅与导电性良好的金属材料复合。一方面金属材料可以改善硅材料的导电性，使得所有的硅在电化学脱嵌锂都起到活性材料的作用，另一方面金属材料可以作为“缓冲骨架”来分散和缓冲硅材料在脱嵌锂过程中体积变化所产生的内应力，使硅金属复合材料具有良好的循环性能。At present, there are two main ways that people propose to solve this problem: One of the methods is to nanometerize silicon. Because with the reduction of particles, the volume change of silicon can be reduced to a certain extent, and the internal stress of the electrode can be reduced. However, nanomaterials are easy to agglomerate during the cycle, which is not enough to improve the performance of the battery for practical use. The second is to combine silicon with metal and other materials, that is, to combine electrochemically active nano-silicon with metal materials with good conductivity. On the one hand, metal materials can improve the conductivity of silicon materials, so that all silicon can play the role of active materials in the electrochemical deintercalation of lithium; The internal stress generated by the volume change during the lithium process makes the silicon-metal composite have good cycle performance.
Wang G.X.等(J.Power.Sources，2000，88：278-281)采用高能球磨法合成了硅／镍和硅／铁合金用于锂离子电池负极材料，硅脱嵌锂的活性物质，镍或铁做为导电骨架的同时也限制了硅在脱嵌锂过程中体积变化带来的结构破坏。Kangkibum等(Chem.Sci.，2011，2：1090)在镍基板上生长硅镍纳米线阵列，在通过气相沉积法在外层沉积硅用于锂离子电池负极材料，内层硅镍纳米线做为骨架，外层硅做为活性材料，在一定程度上抑制了硅材料在脱嵌锂过程中的体积效应，同时改善了硅材料的导电性能，保持了较好的循环性能。Zhang Shichao等(Adv.Mater.2010，22：5378-5382)用类似的方法，在镍纳米锥形阵列外部沉积硅用于锂离子电池负极材料，硅做为活性材料，镍锥形阵列有效地抑制了硅在充放电时的体积变化，从而得到了导电良好，比容量较大且循环性能优良的材料。这些研究表明，纳米硅金属复合材料一般是将金属与硅复合或者硅合金与硅复合形成的，硅金属之间即可以是一种物理结合也可以是化学结合。物理结合对改善硅材料的循环性能帮助不大，而较好的是硅与金属形成化学结合，可以有效改善硅材料本身的体积效应，得到循环性稳定的材料。目前制备这些硅金属复合材料的主要方法包括化学气相沉积法、热气相沉积法、高能球磨等方法。这些制备方法或涉及工艺过程复杂(如模板法)，过程难以控制、所需设备昂贵(如化学气相沉积法)，很难实现批量生产。Wang G.X. et al. (J.Power.Sources, 2000, 88: 278-281) synthesized silicon/nickel and silicon/iron alloys for lithium-ion battery anode materials by high-energy ball milling, active materials for lithium-deintercalation of silicon, nickel or iron As a conductive framework, it also limits the structural damage caused by the volume change of silicon in the process of lithium intercalation and deintercalation. Kangkibum et al. (Chem.Sci., 2011, 2:1090) grow silicon-nickel nanowire arrays on nickel substrates, deposit silicon on the outer layer by vapor deposition for lithium-ion battery negative electrode materials, and inner silicon-nickel nanowires as The skeleton and the outer layer of silicon are used as the active material, which to a certain extent inhibits the volume effect of the silicon material in the process of lithium intercalation and deintercalation, and at the same time improves the conductivity of the silicon material and maintains a good cycle performance. Zhang Shichao et al. (Adv. Mater. 2010, 22: 5378-5382) used a similar method to deposit silicon on the outside of the nickel nano-conical array for lithium-ion battery anode materials. Silicon is used as the active material, and the nickel-conical array is effectively The volume change of silicon during charge and discharge is suppressed, thereby obtaining a material with good conductivity, large specific capacity and excellent cycle performance. These studies show that nano-silicon-metal composite materials are generally formed by compounding metal and silicon or silicon alloy and silicon, and the combination between silicon and metal can be either a physical combination or a chemical combination. Physical combination does not help much to improve the cycle performance of silicon materials, but it is better to form a chemical combination between silicon and metal, which can effectively improve the volume effect of the silicon material itself and obtain a material with stable cycle performance. At present, the main methods for preparing these silicon-metal composite materials include chemical vapor deposition, thermal vapor deposition, high-energy ball milling and other methods. These preparation methods may involve complicated process (such as template method), difficult process control, expensive equipment required (such as chemical vapor deposition method), and it is difficult to realize mass production.
发明内容Contents of the invention
本发明的目的在于克服现有纳米硅金属复合材料硅和金属之间由于物理结合导致用作锂离子电池负极材料时嵌脱锂过程中硅和金属的分离使得此类材料的循环稳定性变差的缺陷，提供一种循环稳定性好的纳米硅金属复合材料，该复合材料以二氧化硅、金属和碳的混合物为原料，通过熔盐电解方法使得二氧化硅电化学还原成纳米硅原位形成纳米硅金属复合材料，由于纳米硅和金属在熔融盐环境下在硅和金属之间可以形成少量硅金属合金，这是一种冶金级的结合。少量的硅金属合金可以限制纳米硅金属复合材料在嵌脱锂过程中体积变化，使得纳米硅金属复合材料中硅和金属不会因为循环次数的增加而彼此分离，从而提高了纳米硅金属复合材料的循环稳定性。本发明同时还提供一种纳米硅金属复合材料的制备方法，该方法生产流程短、无污染、操作简单、原料易得、设备便宜，易于连续生产。The purpose of the present invention is to overcome the separation of silicon and metal in the process of intercalation and extraction of lithium due to physical combination between the existing nano-silicon-metal composite material silicon and metal, which makes the cycle stability of such materials worse. To provide a nano-silicon-metal composite material with good cycle stability, the composite material is made of a mixture of silicon dioxide, metal and carbon, and the silicon dioxide is electrochemically reduced to nano-silicon in situ by molten salt electrolysis. Nano-silicon-metal composites are formed, because nano-silicon and metal can form a small amount of silicon-metal alloy between silicon and metal in a molten salt environment, which is a metallurgical combination. A small amount of silicon-metal alloy can limit the volume change of nano-silicon-metal composites in the process of intercalating and removing lithium, so that silicon and metal in nano-silicon-metal composites will not be separated from each other due to the increase in the number of cycles, thereby improving the performance of nano-silicon-metal composites. cycle stability. The invention also provides a preparation method of nano-silicon-metal composite material, which has short production process, no pollution, simple operation, readily available raw materials, cheap equipment and easy continuous production.
本发明采用以下技术方案：The present invention adopts following technical scheme:
本发明提供一种锂离子电池用纳米硅金属复合材料，该材料至少含有单质硅，第二组成部分，包括过渡金属元素，铝、锡、锑等元素，碱土元素，碳与氧元素，各组分的摩尔百分比例为：5～75mol％的单质硅，25～95mol％的第二组成部分，第二组成部分包括过渡金属、或其组合、或其与硅形成的金属间化合物，铝、锡、锑、或其组合、或其与硅形成的金属间化合物，碱土金属，碳、氧或其与上述元素的化合物元素，0～70mol％的单质碳。其中单质硅的摩尔百分比例进一步优选为10～55mol％。此外，该材料中还可以含有硅氧化合物SiOx，0＜x≤2，其摩尔百分含量为0.1～5mol％的SiOx。上述摩尔比百分比例都是相对于锂离子电池用纳米硅金属复合材料来说。The invention provides a nano-silicon-metal composite material for lithium ion batteries, the material contains at least elemental silicon, the second component includes transition metal elements, elements such as aluminum, tin, antimony, alkaline earth elements, carbon and oxygen elements, each group The molar percentage of the component is: 5-75 mol% of elemental silicon, 25-95 mol% of the second component, the second component includes transition metals, or combinations thereof, or intermetallic compounds formed with silicon, aluminum, tin , antimony, or a combination thereof, or an intermetallic compound formed with silicon, an alkaline earth metal, carbon, oxygen, or a compound element thereof with the above elements, and 0 to 70 mol% of elemental carbon. Among them, the mole percentage of elemental silicon is more preferably 10 to 55 mol%. In addition, the material may also contain silicon oxide compound SiO x , 0<x≤2, and its mole percentage is 0.1-5 mol % SiO x . The above-mentioned molar ratio percentages are all relative to the nano-silicon-metal composite material for lithium-ion batteries.
本发明提供的锂离子电池用纳米硅金属复合材料中单质硅呈线状、颗粒状、管状、片状中的一种或几种；金属成球形、类球形、线状、片状、网状中的一种或几种；单质碳呈球形状、类球形状、片状、线状、管状中的一种或几种。其中，单质硅为纳米硅线、纳米硅颗粒、纳米硅管或纳米硅片中的至少一种。并且，颗粒状单质硅的粒径小于100nm，线状单质硅的直径小于100nm，管状单质硅的直径小于100nm，片状单质硅的厚度小于100nm。In the nano-silicon-metal composite material for lithium ion batteries provided by the present invention, the elemental silicon is in one or more of linear, granular, tubular, and sheet shapes; the metal is in a spherical, spherical, linear, sheet, or mesh shape. One or more of them; elemental carbon is one or more of spherical shape, spherical shape, flake shape, linear shape, and tubular shape. Wherein, the elemental silicon is at least one of nano-silicon wires, nano-silicon particles, nano-silicon tubes or nano-silicon sheets. Moreover, the particle diameter of granular elemental silicon is less than 100 nm, the diameter of linear elemental silicon is less than 100 nm, the diameter of tubular elemental silicon is less than 100 nm, and the thickness of sheet-like elemental silicon is less than 100 nm.
本发明提供一种纳米硅金属复合材料的制备方法，其具体步骤是：以二氧化硅和金属材料组成的多孔块体与导电的阴极集流体复合作为阴极，以石墨或惰性阳极作为阳极，置于以CaCl2或以CaCl2为主的混盐熔体电解质中，在阴极和阳极之间施加电压，控制电解时间，使得多孔块体中的二氧化硅电解还原成纳米硅，在阴极制得纳米硅金属复合材料。The invention provides a method for preparing a nano-silicon-metal composite material. The specific steps are: composite a porous block composed of silicon dioxide and a metal material with a conductive cathode current collector as the cathode, and use graphite or an inert anode as the anode, and place the In the mixed salt melt electrolyte mainly composed of CaCl 2 or CaCl 2 , a voltage is applied between the cathode and the anode, and the electrolysis time is controlled, so that the silicon dioxide in the porous block is electrolytically reduced to nano-silicon, which is produced at the cathode Nano-silicon-metal composites.
所述二氧化硅粒径为10nm至1μm。The particle size of the silicon dioxide is 10 nm to 1 μm.
所述二氧化硅和金属组成的多孔块体是指将二氧化硅粉末首先制成二氧化硅胶体，胶体制备时，二氧化硅与水质量比为，二氧化硅20～50wt％，水50～80wt％。将金属加入到二氧化硅胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10～200MPa，多孔块体制成温度为800～1400℃，得到的多孔块体的孔隙率为1～40体积％，多孔块体的孔隙率进一步优选为10～30体积％，密度0.5～2.0g／cm3，电阻率0.1-2Ω·cmThe porous block composed of silicon dioxide and metal means that silicon dioxide powder is first made into silicon dioxide colloid. When the colloid is prepared, the mass ratio of silicon dioxide to water is 20% to 50% by weight of silicon dioxide and 50% by weight of water. ~80wt%. The metal is added to the silica colloid, and it is mechanically fused at a high speed, so that the silica is uniformly coated on the metal to form a mixture, and then the mixture is made into a block green body, and the block green body is subjected to a certain mechanical pressure or a certain The porous block is formed at high temperature, the mechanical pressure of the porous block is 10-200MPa, the temperature of the porous block is 800-1400°C, the porosity of the obtained porous block is 1-40% by volume, and the porosity of the porous block is More preferably 10-30% by volume, density 0.5-2.0g/cm 3 , resistivity 0.1-2Ω·cm
所述二氧化硅和金属氧化物组成的多孔块体是指将二氧化硅粉末首先制成二氧化硅胶体，将金属氧化物加入到二氧化硅胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属氧化物上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10～200MPa，多孔块体制成温度为800～1400℃，得到的多孔块体的孔隙率为1～40体积％，多孔块体的孔隙率进一步优选为10～30体积％。The porous block composed of silicon dioxide and metal oxide means that the silicon dioxide powder is first made into silicon dioxide colloid, and the metal oxide is added to the silicon dioxide colloid, followed by high-speed mechanical fusion, so that the silicon dioxide Silicon is evenly coated on the metal oxide to form a mixture, and then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 10-200MPa The temperature for forming the porous block is 800-1400°C, and the porosity of the obtained porous block is 1-40% by volume, and the porosity of the porous block is more preferably 10-30% by volume.
所述二氧化硅、金属和碳组成的多孔块体是指将二氧化硅粉末首先制成二氧化硅胶体，将碳和金属加入到二氧化硅胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10～200MPa，多孔块体制成温度为800～1400℃，得到的多孔块体的孔隙率为1～40％，多孔块体的孔隙率进一步优选为10～30体积％。The porous block composed of silicon dioxide, metal and carbon means that silicon dioxide powder is first made into silica colloid, carbon and metal are added to silica colloid, and high-speed mechanical fusion is performed to make the silica colloid Silicon is evenly coated on metal and carbon to form a mixture, and then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 10-200MPa The manufacturing temperature of the porous block is 800-1400° C., and the porosity of the obtained porous block is 1-40%, and the porosity of the porous block is more preferably 10-30% by volume.
所述二氧化硅、金属氧化物和碳组成的多孔块体是指将二氧化硅粉末首先制成二氧化硅胶体，将碳和金属氧化物加入到二氧化硅胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10～200MPa，多孔块体制成温度为800～1400℃，得到的多孔块体的孔隙率为1～40体积％，多孔块体的孔隙率进一步优选为10～30体积％。The porous block composed of silicon dioxide, metal oxide and carbon means that the silicon dioxide powder is first made into silica colloid, and carbon and metal oxide are added to the silica colloid, followed by high-speed mechanical fusion , so that the silicon dioxide is evenly coated on the metal oxide and carbon to form a mixture, and then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature, and the porous block is made of The mechanical pressure is 10-200MPa, the temperature for forming the porous block is 800-1400°C, and the porosity of the obtained porous block is 1-40% by volume, and the porosity of the porous block is more preferably 10-30% by volume.
所述以CaCl2为主的混盐熔体电解质为CaCl2+MY1，其中M为Ba、Li、Al、Cs、Na、K、Mg、Rb、Be或Sr，Y1为Cl或F。The mixed salt melt electrolyte mainly composed of CaCl 2 is CaCl 2 +MY 1 , wherein M is Ba, Li, Al, Cs, Na, K, Mg, Rb, Be or Sr, and Y 1 is Cl or F.
所述电压低于电解质的理论分解电压，电解时间为电解电量达到理论所需电量及以上。理论分解电压为SiO2在熔盐中的理论计算分解电压，其随熔盐成份和温度变化而变化。理论所需电量为根据SiO2变成单质Si所消耗电子计算的电量，其随SiO2含量变化而变化。The voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis time is when the electrolysis electric quantity reaches the theoretical required electric quantity and above. Theoretical decomposition voltage is the theoretically calculated decomposition voltage of SiO2 in molten salt, which changes with the composition and temperature of molten salt. The theoretical required electricity is the electricity calculated based on the electrons consumed by SiO2 into simple Si, which changes with the change of SiO2 content.
电解在500-1000℃的温度下进行。Electrolysis is carried out at a temperature of 500-1000°C.
本发明提供了一种锂离子电池，该电池包括正极、负极及非水电解液，所述负极包括本发明中所述纳米硅金属复合材料。The invention provides a lithium ion battery, which comprises a positive pole, a negative pole and a non-aqueous electrolyte, and the negative pole comprises the nano-silicon-metal composite material in the invention.
本发明具备如下特点：The present invention has following characteristics:
(1)通过调节原料二氧化硅和金属的比例可以调节纳米硅金属复合材料中的硅金属比例，纳米硅金属复合材料的嵌锂容量即比容量可以调节；(1) The proportion of silicon and metal in the nano-silicon-metal composite can be adjusted by adjusting the ratio of the raw material silicon dioxide and metal, and the lithium intercalation capacity of the nano-silicon-metal composite, that is, the specific capacity, can be adjusted;
(2)通过控制电解电量可以调节电解产物纳米硅金属复合材料中硅合金和硅氧化物含量，控制硅和金属之间的冶金结合程度，从而提高纳米硅金属复合材料的电化学循环稳定性；(2) By controlling the amount of electrolysis, the content of silicon alloy and silicon oxide in the electrolysis product nano-silicon-metal composite can be adjusted, and the degree of metallurgical bonding between silicon and metal can be controlled, thereby improving the electrochemical cycle stability of the nano-silicon-metal composite;
(3)所用原料来源丰富，价格便宜，原材料及制备过程均对环境无污染；(3) The source of raw materials used is abundant, the price is cheap, and the raw materials and the preparation process are all non-polluting to the environment;
(4)工艺过程简单，操作简便，设备简易；(4) The process is simple, the operation is easy and the equipment is simple;
(5)原料和产物均以固态形式加入或移出，易于实现连续化生产。(5) Both raw materials and products are added or removed in solid form, which is easy to realize continuous production.
附图说明Description of drawings
附图1为实施例1以镍粉、氧化亚镍与二氧化硅混合物为原料在900℃下本发明制备纳米硅基金属复合材料的扫描电子显微镜图像。Accompanying drawing 1 is the scanning electron microscope image of the nano-silicon-based metal composite material prepared by the present invention at 900° C. using a mixture of nickel powder, nickelous oxide and silicon dioxide as raw materials in Example 1.
附图2为实施例16以球状碳、镍粉、氧化亚镍与二氧化硅混合物为原料在950℃下本发明制备硅基金属碳纳米线复合材料的扫描电子显微镜图像。Accompanying drawing 2 is the scanning electron microscope image of the silicon-based metal-carbon nanowire composite material prepared by the present invention at 950° C. using spherical carbon, nickel powder, nickelous oxide and silicon dioxide mixture as raw materials in Example 16.
附图3为实施例2在900℃下本发明制备的纳米硅金属复合材料的X射线衍射图谱。Accompanying drawing 3 is the X-ray diffraction spectrum of the nano-silicon-metal composite material prepared by the present invention at 900°C in Example 2.
具体实施方式Detailed ways
下面将进一步结合附图和实施例对本发明进行描述。这些描述只是为了进一步对本发明进行说明，而不是对本发明进行限制。The present invention will be further described below in conjunction with the accompanying drawings and embodiments. These descriptions are only for further illustrating the present invention, rather than limiting the present invention.
本发明提供一种锂离子电池用纳米硅金属复合材料，该材料中至少含有单质硅和金属。该材料中的单质硅是通过电化学方法熔盐电解原料中的二氧化硅而得到的，金属来源于原料中的金属和电解金属氧化物得到的，而单质碳来源于原料中的单质碳。因此可以通过调节原料中二氧化硅、金属和金属氧化物与碳的比例来调节纳米硅金属复合材料中的单质硅和金属或碳的比例。通过控制纳米硅金属复合材料中单质硅、金属和碳的比例可以调节该材料的比例可以调节该材料的嵌锂容量。硅含量过低，纳米硅金属复合材料的比容量太低，不能满足电池需求。硅比例过高，在其他条件完全相同的情况下，该纳米硅金属复合材料的比容量也越高，但由于部分单质硅不能与金属形成有效结合而使得硅因脱嵌锂导致的体积变化也越厉害，从而导致使用该纳米硅金属复合材料的电池的循环性能也越差。因此，纳米硅金属复合材料中单质硅的摩尔百分含量至少10％、至少15％、或至少20％；单质硅的摩尔百分含量也可以高达35％、高达40％、高达45％、高达50％、或高达55％。例如纳米硅金属复合材料中单质硅的摩尔百分含量可以为10～55％、10～45％、10～35％、10～25％、15～55％、15～45％、15～35％、15～25％、20～55％、20～45％、20～35％、20～25％、30～55％、30～45％、30～35％、40～55％、40～45％或50～55％。The invention provides a nano-silicon-metal composite material for a lithium ion battery, which contains at least elemental silicon and metal. The elemental silicon in this material is obtained by electrochemically molten salt electrolysis of silicon dioxide in the raw material, the metal is obtained from the metal in the raw material and electrolytic metal oxide, and the elemental carbon is derived from the elemental carbon in the raw material. Therefore, the ratio of elemental silicon and metal or carbon in the nano-silicon-metal composite can be adjusted by adjusting the ratio of silicon dioxide, metal, metal oxide and carbon in the raw materials. By controlling the ratio of simple silicon, metal and carbon in the nano-silicon-metal composite material, the ratio of the material can be adjusted to adjust the lithium intercalation capacity of the material. If the silicon content is too low, the specific capacity of the nano-silicon-metal composite is too low to meet the needs of batteries. If the proportion of silicon is too high, the specific capacity of the nano-silicon-metal composite material will be higher under other identical conditions. The worse it is, the worse the cycle performance of the battery using the nano-silicon-metal composite material will be. Therefore, the molar percentage of elemental silicon in the nano-silicon metal composite material is at least 10%, at least 15%, or at least 20%; the molar percentage of elemental silicon can also be as high as 35%, up to 40%, up to 45%, up to 50%, or as high as 55%. For example, the mole percentage of elemental silicon in the nano-silicon-metal composite material can be 10-55%, 10-45%, 10-35%, 10-25%, 15-55%, 15-45%, 15-35%. , 15~25%, 20~55%, 20~45%, 20~35%, 20~25%, 30~55%, 30~45%, 30~35%, 40~55%, 40~45% Or 50-55%.
所述的纳米硅金属复合材料中第二组成部分可包含过渡金属、或其组合、或其与硅形成的化合物的第一成分，可包含铝、锡、锑、或其组合、或其与硅形成的化合物合的第二成分，可包含碱土元素或其组合的第三成分，还可包含由碳、氧、或他们与硅或第一、第二、第三成分组成的化合物组成的第四成分。第二组成部分的摩尔百分含量至少10％、至少15％、至少20％、至少25％、或至少30％；第二成分的摩尔百分含量也可以高达50％、高达55％、高达60％、高达65％、高达70％、高达75％、高达80％、高达85％、或高达90％。第二组成部分中的一些金属具有电化学活性，能够提供一部分容量，而其他一部分金属不具备电化学活性，因此，第二成分的摩尔百分含量进一步优选为10～70％。例如第二成分的摩尔百分含量可以为10～20％、10～30％、10～40％、10～50％、10～60％、10～70％、20～30％、20～40％、20～50％、20～60％、20～70％、30～40％、30～50％、30～60％、30～70％、40～50％、40～60％或40～70％。The second component in the nano-silicon-metal composite material may include the first component of a transition metal, or a combination thereof, or a compound formed with silicon, and may include aluminum, tin, antimony, or a combination thereof, or a combination thereof with silicon. The second component of the formed compound may include a third component of alkaline earth elements or a combination thereof, and may also include a fourth component composed of carbon, oxygen, or their compounds with silicon or the first, second, and third components. Element. The molar percentage of the second component is at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%; the molar percentage of the second component can also be up to 50%, up to 55%, up to 60% %, up to 65%, up to 70%, up to 75%, up to 80%, up to 85%, or up to 90%. Some metals in the second component are electrochemically active and can provide part of the capacity, while other metals are not electrochemically active. Therefore, the molar percentage of the second component is further preferably 10-70%. For example, the molar percentage of the second component can be 10-20%, 10-30%, 10-40%, 10-50%, 10-60%, 10-70%, 20-30%, 20-40% , 20～50%, 20～60%, 20～70%, 30～40%, 30～50%, 30～60%, 30～70%, 40～50%, 40～60% or 40～70% .
纳米硅金属复合材料中的硅氧化合物SiOx来源于原料中未完全还原的二氧化硅或电解产物纳米硅金属复合材料中的单质硅在后处理过程中被再次氧化，因此硅氧化合物附着在单质硅表面。通过控制电解电量即电解时间可以调节电解产物纳米硅金属复合材料中硅氧化合物的含量。如控制电解时间足够使得原料二氧化硅彻底电解，此时纳米硅金属复合材料中不含硅氧化合物。纳米硅金属复合材料中硅氧化物由于能嵌锂，嵌锂后形成的附着在纳米硅表面硅酸锂不但具有良好的导电性，并且能够有效限制硅嵌脱锂过程中的体积变化。因此，纳米硅金属复合材料中的硅氧化合物有利于提高硅金属复合材料的循环稳定性，但由于硅氧化合物嵌锂后形成的硅酸锂不能完全将锂脱出，因此使得纳米硅金属复合材料的首次库伦效率较低。因此，纳米硅金属复合材料中硅氧化合物的摩尔百分含量为0.1～5mol％。The silicon oxide compound SiOx in the nano-silicon metal composite material is derived from the incompletely reduced silicon dioxide in the raw material or the electrolysis product. The elemental silicon in the nano-silicon metal composite material is oxidized again during the post-treatment process, so the silicon oxide compound is attached to the Elemental silicon surface. The content of the silicon oxide compound in the electrolysis product nano-silicon-metal composite material can be adjusted by controlling the electrolysis electric quantity, that is, the electrolysis time. If the electrolysis time is controlled enough to completely electrolyze the silicon dioxide as the raw material, the nano-silicon-metal composite does not contain silicon-oxygen compounds. Since silicon oxide in the nano-silicon metal composite material can intercalate lithium, the lithium silicate attached to the surface of nano-silicon formed after intercalation of lithium not only has good conductivity, but also can effectively limit the volume change in the process of silicon intercalation and delithiation. Therefore, the silicon-oxygen compound in the nano-silicon-metal composite material is beneficial to improve the cycle stability of the silicon-metal composite material, but since the lithium silicate formed after the silicon-oxygen compound intercalates lithium cannot completely remove lithium, the nano-silicon-metal composite material The first Coulombic efficiency is low. Therefore, the mole percentage of the silicon-oxygen compound in the nano-silicon-metal composite material is 0.1-5 mol%.
本发明的纳米硅金属复合材料具有以下结构特征：金属呈球状、类球状、片状、线状中的一种或几种；单质硅呈线状、颗粒状、管状、片状中的一种或几种。其中，单质硅为纳米硅线、纳米硅颗粒、纳米硅管、纳米硅片中的至少一种。并且，颗粒状单质硅的粒径小于100nm，线状单质硅的直径小于100nm，管状单质硅的直径小于100nm，片状单质硅的厚度小于100nm。单质碳呈球形状、类球形状、片状、线状、管状中的一种或几种。纳米硅金属复合材料的结构以各组成部分的结构相关，包含但可以不与各组成部分的结构完全一致。The nano-silicon-metal composite material of the present invention has the following structural features: the metal is one or more of spherical, spherical, sheet-like, and wire-like; the elemental silicon is one of wire-like, granular, tubular, and sheet-like or several. Wherein, the elemental silicon is at least one of nano-silicon wires, nano-silicon particles, nano-silicon tubes, and nano-silicon chips. Moreover, the particle diameter of granular elemental silicon is less than 100 nm, the diameter of linear elemental silicon is less than 100 nm, the diameter of tubular elemental silicon is less than 100 nm, and the thickness of sheet-like elemental silicon is less than 100 nm. Elemental carbon is one or more of spherical shape, spherical shape, flake shape, linear shape, and tubular shape. The structure of the nano-silicon-metal composite material is related to the structure of each component, including but may not be completely consistent with the structure of each component.
纳米硅金属复合材料中的金属来源于原料中的金属和金属氧化物，可以为结晶和／或无定形状；纳米硅金属复合材料中的单质碳来源于原料中的碳材料，可以为锂离子电池领域常用的石墨类负极材料，如天然石墨、人造石墨、中间相碳微球等；也可以是锂离子电池用的导电类碳材料，如乙炔黑、碳黑、碳纤维或碳管等，也可以是有机物热解碳，如聚乙烯醇、丁苯橡胶乳、羧甲基纤维素、聚甲基丙烯酸酯、聚四氟乙烯、聚偏氟乙烯、聚丙烯腈、酚醛树脂、环氧树脂、葡萄糖、蔗糖、果糖、纤维素、淀粉或沥青等。The metal in the nano-silicon-metal composite material is derived from the metal and metal oxide in the raw material, which can be crystalline and/or amorphous; the elemental carbon in the nano-silicon-metal composite material is derived from the carbon material in the raw material, which can be lithium ion Graphite negative electrode materials commonly used in the battery field, such as natural graphite, artificial graphite, mesocarbon microspheres, etc.; can also be conductive carbon materials for lithium-ion batteries, such as acetylene black, carbon black, carbon fiber or carbon tubes, etc. It can be organic pyrolytic carbon, such as polyvinyl alcohol, styrene-butadiene rubber latex, carboxymethyl cellulose, polymethacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, phenolic resin, epoxy resin, Glucose, sucrose, fructose, cellulose, starch or asphalt, etc.
纳米硅金属复合材料中的金属会与硅生成金属硅化物，主要为电极烧结过程中金属还原二氧化硅或熔融盐中纳米硅与金属长时间浸泡缓慢生成。金属硅化物能够有效提高单质硅与金属的结合力，提高导电性，并抑制硅材料在脱嵌锂过程中过大的体积变化。因此保证原料中二氧化硅和金属材料的均匀性，能够保证生成的硅、金属与金属硅化物可以均匀的结合在一起。The metal in the nano-silicon-metal composite material will form metal silicide with silicon, which is mainly formed slowly by soaking nano-silicon and metal in the metal-reduced silica or molten salt for a long time during the electrode sintering process. Metal silicides can effectively improve the bonding force between elemental silicon and metal, improve electrical conductivity, and inhibit the excessive volume change of silicon materials during the process of lithium intercalation and deintercalation. Therefore, ensuring the uniformity of silicon dioxide and metal materials in the raw materials can ensure that the generated silicon, metal and metal silicide can be uniformly combined.
本发明提供的纳米硅金属复合材料的制备方法包括以下步骤：The preparation method of the nano-silicon-metal composite material provided by the invention comprises the following steps:
1.将以金属和金属氧化物和二氧化硅组成的多孔块体与导电的阴极集流体复合作为阴极，以石墨或惰性阳极作为阳极，置于一定温度下以CaCl2或以CaCl2为主的混盐熔体电解质中，在阴极和阳极之间施加电压，电解电量作为电解过程结束控制手段，使得多孔块体中的二氧化硅电解还原成纳米硅，在阴极制得纳米硅金属复合材料。电解时间为电解电量达到理论所需电量及以上。理论所需电量为根据SiO2变成单质Si所消耗电子计算的电量，其随SiO2含量变化而变化。1. Combining a porous block composed of metal, metal oxide and silicon dioxide with a conductive cathode current collector as the cathode, using graphite or an inert anode as the anode, and placing it at a certain temperature with CaCl 2 or CaCl 2 as the main In the mixed salt melt electrolyte, a voltage is applied between the cathode and the anode, and the electrolytic power is used as a means of controlling the end of the electrolysis process, so that the silicon dioxide in the porous block is electrolytically reduced to nano-silicon, and the nano-silicon-metal composite material is prepared at the cathode . The electrolysis time is when the electrolysis power reaches the theoretical required power and above. The theoretical required electricity is the electricity calculated based on the electrons consumed by SiO2 into simple Si, which changes with the change of SiO2 content.
所述以金属和金属氧化物和二氧化硅组成的多孔块体的结构(如微观均匀性、孔隙率、孔径)、组成和尺寸是影响电解产物纳米硅金属复合材料的单质硅、金属、金属硅化物及硅氧化合物的组成比例、形貌、分布均匀性及作为锂离子电池负极材料的比容量的关键因素。以金属、金属氧化物和二氧化硅组成的多孔块体中金属、金属氧化物和二氧化硅的微观均匀性会直接影响电解产物纳米硅金属复合材料的单质硅、金属和金属硅化物分布的均匀性，因此，必须制作混合均匀的多孔块体。金属和二氧化硅组成的多孔电块体的孔隙率较大时，例如多孔块体孔隙率大于60％时，电解过程中由于二氧化硅电解还原生成硅由于氧的脱出会造成体积缩小50％，还原后由金属和硅组成的多孔块体孔隙率的增大，使得多孔块体强度不够而不能完整的从熔盐中取出。金属和二氧化硅组成的多孔块体的孔隙率较较小时，例如多孔块体孔隙率小于5体积％时，多孔块体中能供熔融电解质氯化钙通过的孔隙较少，电解还原反应速度降低，电解时间过长，导致产物中金属硅化物含量过多。The structure (such as microscopic uniformity, porosity, pore size), composition and size of the porous block composed of metal, metal oxide and silicon dioxide is the elemental silicon, metal, and metal that affect the electrolysis product nano-silicon-metal composite material. The composition ratio, morphology, and uniformity of distribution of silicide and silicon-oxygen compound are the key factors for the specific capacity of lithium-ion battery negative electrode materials. The micro-uniformity of metal, metal oxide and silicon dioxide in the porous block composed of metal, metal oxide and silicon dioxide will directly affect the distribution of elemental silicon, metal and metal silicide in the electrolysis product nano-silicon-metal composite. Uniformity, therefore, must produce porous masses that are well mixed. When the porosity of the porous electrical block composed of metal and silicon dioxide is large, for example, when the porosity of the porous block is greater than 60%, the volume of silicon will be reduced by 50% due to the electrolytic reduction of silicon dioxide during the electrolysis process due to the release of oxygen. , the porosity of the porous block composed of metal and silicon increases after reduction, making the porous block not strong enough to be completely removed from the molten salt. When the porosity of the porous block composed of metal and silicon dioxide is relatively small, for example, when the porosity of the porous block is less than 5% by volume, there are fewer pores in the porous block that can pass through the molten electrolyte calcium chloride, and the electrolytic reduction reaction speed Reduced, the electrolysis time is too long, resulting in too much metal silicide content in the product.
将以金属和金属氧化物和二氧化硅组成的多孔块体与导电的阴极集流体复合作为阴极的具体实施过程是将二氧化硅粉末首先制成二氧化硅胶体，将金属和金属氧化物加入到二氧化硅胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属氧化物和金属上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10～100MPa，多孔块体制成温度为800～1400℃，得到的多孔块体的孔隙率为10～30％。The specific implementation process of combining a porous block composed of metal, metal oxide and silicon dioxide with a conductive cathode current collector as a cathode is to first make silicon dioxide powder into silicon dioxide colloid, and then add metal and metal oxide into the silica colloid, and high-speed mechanical fusion, so that the silica is evenly coated on the metal oxide and metal to form a mixture, and then the mixture is made into a block green body, and the block green body is subjected to a certain mechanical pressure or The porous block is formed at a certain temperature, the mechanical pressure of the porous block is 10-100MPa, the temperature of the porous block is 800-1400°C, and the porosity of the obtained porous block is 10-30%.
2.根据步骤1所述的制备方法，所述原料中的金属粉末呈球状、类球状、片状、或线状。2. According to the preparation method described in step 1, the metal powder in the raw material is in the shape of a sphere, a spheroid, a flake, or a wire.
3．根据步骤1诉说的制备方法，所述原料中的金属氧化物呈粉末状。3. According to the preparation method described in step 1, the metal oxides in the raw materials are in powder form.
4．根据步骤1所述的制备方法，所述二氧化硅粉末是指平均粒径10nm至1μm的二氧化硅颗粒。4. According to the preparation method described in step 1, the silica powder refers to silica particles with an average particle diameter of 10 nm to 1 μm.
5．根据步骤1所述的制备方法，所述以CaCl2为主的混盐熔体电解质为CaCl2+MY1，其中M是指Ba、Li、Al、Cs、Na、K、Mg、Rb、Be或Sr，Y1为Cl或F。5. According to the preparation method described in step 1, the mixed salt melt electrolyte mainly composed of CaCl 2 is CaCl 2 +MY 1 , wherein M refers to Ba, Li, Al, Cs, Na, K, Mg, Rb, Be Or Sr, Y 1 is Cl or F.
6.根据步骤1所述的制备方法，所述电解电压为低于电解质的理论分解电压，电解电量为电解电量达到理论所需电量及以上。6. According to the preparation method described in step 1, the electrolysis voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis power is that the electrolysis power reaches the theoretical required power and above.
7.根据步骤1所述的制备方法，电解在500-1000℃的温度下进行。7. According to the preparation method described in step 1, the electrolysis is carried out at a temperature of 500-1000°C.
8.根据步骤1所述的制备方法，电解过程完成后，产物即可随工作电极从熔盐中取出，如有必要可放入以金属或金属氧化物和二氧化硅组成的多孔块体电极开始新一轮电解，从而实现纳米硅金属复合材料的连续生产。8. According to the preparation method described in step 1, after the electrolysis process is completed, the product can be taken out from the molten salt along with the working electrode, and if necessary, it can be placed in a porous block electrode composed of metal or metal oxide and silicon dioxide Start a new round of electrolysis, so as to realize the continuous production of nano-silicon metal composite materials.
9．根据步骤1所述的制备方法，电解产物取出后，在惰性气氛下冷却至室温，然后在水和有机溶剂中充分洗涤，出去产物中夹杂的熔盐电解质。9. According to the preparation method described in step 1, after the electrolysis product is taken out, it is cooled to room temperature under an inert atmosphere, and then fully washed in water and an organic solvent to remove the molten salt electrolyte entrapped in the product.
10.根据步骤1所述的制备方法，洗净后的电解产物在真空中干燥12h以上。10. According to the preparation method described in step 1, the washed electrolytic product is dried in vacuum for more than 12 hours.
11.根据步骤1所述的制备方法，干燥后的电解产物研磨破碎，过筛后得到纳米硅金属复合材料。11. According to the preparation method described in step 1, the dried electrolysis product is ground and crushed, and the nano-silicon-metal composite material is obtained after sieving.
下面的实施例用以说明本发明，实施例所述的原料中的“纳米SiO2粉末”是指粒径在100nm以下的粉末。The following examples are used to illustrate the present invention, and "nano- SiO2 powder" in the raw materials described in the examples refers to powders with a particle diameter below 100nm.
实施例1Example 1
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将30mol％的市售直径为2～10μm的类球状镍粉10mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为14MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为30体积％，密度为1.3g／cm3，电导率为0.8Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.2V。经过8小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物如附图1所示的镍负载纳米硅颗粒复合材料，硅化镍间断存在于镍和纳米硅颗粒之间，硅氧化物SiOx存在于纳米硅颗粒表面。所制备的镍负载纳米硅颗粒复合材料中单质镍摩尔百分含量为38％，单质硅摩尔百分含量55％，硅化镍(NiSi2)摩尔百分含量5％，硅氧化合物SiO22％，记为55Si／45(Ni38(NiSi2)5(giO2)2)。所述复合材料中单质硅呈结晶状，单质硅呈颗粒状和线状，颗粒状单质硅的粒径小于100nm，线状单质硅的直径小于100nm。60mol% of nano- SiO2 powder with a purity of 99.95wt% is added with water and stirred to form silica colloid. % Commercially available nickel suboxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body, and the block green body A porous block is formed under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 14MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 30% by volume, and the density is 1.3g/ cm 3 , the conductivity is 0.8Ω·cm, the porous block and the conductive cathode current collector are combined as the cathode, the graphite rod is used as the anode, and the CaCl 2 is used as the electrolyte. The voltage regulator controls the voltage for constant voltage electrolysis, and the cell voltage is 2.2V. After 8 hours of electrolysis, the electrolyzed product was rinsed with water and absolute ethanol successively, vacuum-dried, and sieved to obtain the nickel-supported nano-silicon particle composite material as shown in Figure 1. Nickel silicide is intermittently present between nickel and nano-silicon particles In between, silicon oxide SiOx exists on the surface of nano-silicon particles. The prepared nickel-supported nano-silicon particle composite material has a molar percentage of elemental nickel of 38%, a molar percentage of elemental silicon of 55%, a molar percentage of nickel silicide (NiSi 2 ), and a silicon oxide compound SiO 2 of 2%. , recorded as 55Si/45 (Ni 38 (NiSi 2 ) 5 (giO 2 ) 2 ). The elemental silicon in the composite material is crystallized, the elemental silicon is granular and linear, the particle diameter of the granular elemental silicon is less than 100nm, and the diameter of the linear elemental silicon is less than 100nm.
所得复合材料按下述方法制备锂离子电池电极：以制得的电解产物纳米硅镍复合材料为活性物质，Super-P炭黑为导电剂，PVDF为粘结剂，按质量比7：2：1混合均匀后，用N-甲基吡咯烷酮为溶剂调浆，将浆料涂覆在8μm厚的铜箔上制成1.0cm×1.5cm的极片，在70℃干燥后辊压至极片所需厚度，在120℃真空下干燥12h，备用。以金属锂片为对电极，Celgard2300膜为隔膜，1mol／LLiPF6／EC+DEC+DMC(体积比1：1：1)为电解液组装实验电池(自行设计、直径Φ＝30mm，长L＝100mm)。用蓝电电池测试系统CT2001A测试仪测试实验电池的充放电性能。充放电电压范围为0.005～2.0V，充放电电流密度80mA／g，测试电池循环100周的容量保持率C100／C1。The resulting composite material is prepared as an electrode for a lithium-ion battery as follows: the obtained electrolysis product nano-silicon-nickel composite material is used as an active material, Super-P carbon black is used as a conductive agent, and PVDF is used as a binder, in a mass ratio of 7:2: 1 After mixing evenly, use N-methylpyrrolidone as a solvent to prepare the slurry, coat the slurry on an 8μm thick copper foil to make a 1.0cm×1.5cm pole piece, dry it at 70°C and roll it to the pole piece required thickness, dried under vacuum at 120°C for 12 hours, and set aside. The lithium metal sheet was used as the counter electrode, the Celgard2300 film was used as the separator, and 1mol/LLiPF 6 /EC+DEC+DMC (volume ratio 1:1:1) was used as the electrolyte to assemble the experimental battery (self-designed, diameter Φ=30mm, length L= 100mm). The charge and discharge performance of the experimental battery was tested with the CT2001A tester of the blue electric battery test system. The charge-discharge voltage range is 0.005-2.0V, the charge-discharge current density is 80mA/g, and the capacity retention rate C 100 /C 1 of the battery is tested for 100 cycles.
实施例2Example 2
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉和20mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为14MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为23体积％，密度为1.4g／cm3，电导率为1.2Ω2·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.4V。经过7小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料53Si／47(Ni35(NiSi2)8(SiO2)4)。如图3，所得复合材料中的结晶成份以单质Si、Ni和NiSi化合物为主。60mol% of nano- SiO2 powder with a purity of 99.95wt% was stirred with water to form colloidal silica, the mass ratio of water and SiO2 was 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm and 20mol% of commercially available nickel oxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body. The billet forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 14MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 23% by volume and the density is 1.4g. /cm 3 , the electrical conductivity is 1.2Ω2·cm, the porous block is combined with the conductive cathode current collector as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon atmosphere, the temperature is 850°C. The constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.4V. After 7 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the nickel powder-supported nano-silicon particle composite material 53Si/47 (Ni 35 (NiSi 2 ) 8 (SiO 2 ) 4 ). As shown in Figure 3, the crystalline components in the obtained composite material are mainly simple Si, Ni and NiSi compounds.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例3Example 3
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉30mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为14MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为15体积％，密度为1.25g／cm3，电导率为1.5Ω2·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过6小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载硅纳米线复合材料45Si／55(Ni48(NiSi)5(SiO2)2)。50mol% of nano- SiO2 powder with a purity of 99.95wt% is added with water and stirred to form colloidal silica, the mass ratio of water to SiO2 is 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm is 30mol % Commercially available nickel suboxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body, and the block green body A porous block is formed under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 14MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 15% by volume, and the density is 1.25g/ cm 3 , the electrical conductivity is 1.5Ω2·cm, the porous block is combined with the conductive cathode current collector as the cathode, the graphite rod is used as the anode, and the CaCl 2 is used as the electrolyte. The voltage regulator controls the voltage for constant voltage electrolysis, and the cell voltage is 2.5V. After 6 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain a nickel powder-supported silicon nanowire composite material 45Si/55 (Ni 48 (NiSi) 5 (SiO 2 ) 2 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例4Example 4
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将40mol％的市售直径为2～10μm的类球状镍粉10mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为14MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为29体积％，密度为1.5g／cm3，电导率为0.4Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为800℃，用稳压器控制电压进行恒电压电解，槽电压为2.8V。经过18小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉上生长纳米硅线复合材料40Si／60(Ni42(NiSi)15(SiO2)3)。50mol% of nano- SiO2 powder with a purity of 99.95wt% is added with water and stirred to form colloidal silica. % Commercially available nickel suboxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body, and the block green body A porous block is formed under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 14MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 29% by volume, and the density is 1.5g/ cm 3 , the conductivity is 0.4Ω·cm, the porous block and the conductive cathode current collector are combined as the cathode, the graphite rod is used as the anode, and the CaCl 2 is used as the electrolyte. The voltage regulator controls the voltage for constant voltage electrolysis, and the cell voltage is 2.8V. After 18 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain a composite material 40Si/60(Ni 42 (NiSi) 15 (SiO 2 ) 3 ) grown on nickel powder with nanometer silicon wires.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例5Example 5
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为1～5μm的镍纤维及10mol％球状铁粉和10mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为15MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为25体积％，密度为1.1g／cm3，电导率为0.2Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.8V。经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到硅金属纳米线复合材料54Si／46(Ni27Fe8(NiSi2)5(FeSi2)2(Fe2O3)2(SiO2)2)。60mol% of nano -SiO2 powder with a purity of 99.95wt% was added with water and stirred to form colloidal silica, the mass ratio of water to SiO2 was 2:1, 20mol% of commercially available nickel fibers with a diameter of Spherical iron powder and 10mol% commercially available nickel oxide with a purity of 98wt% are added to the colloid, and combined with high-speed machinery, so that silicon dioxide is evenly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body The green body of the block forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 15 MPa, and the temperature of the porous block is 900 ° C. The porosity of the obtained porous block is 25% by volume. The density is 1.1g/cm 3 , the conductivity is 0.2Ω·cm, the composite porous block and the conductive cathode current collector are used as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In the environment of argon, the temperature The temperature is 850°C, and the constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolyzed product was washed with water and ethanol in sequence, dried in vacuum, and sieved to obtain the silicon-metal nanowire composite material 54Si/46(Ni 27 Fe 8 (NiSi 2 ) 5 (FeSi 2 ) 2 (Fe 2 O 3 ) 2 (SiO 2 ) 2 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例6Example 6
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将12mol％的市售直径为1～5μm的镍纤维及20mol％球状铁粉和8mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为20MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为15体积％，密度为1.2g／cm3，电导率为1.2Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.8V。经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到硅金属纳米线复合材料52Si／48(Ni18Fe17(NiSi2)3(FeSi2)4(Fe2O3)5(SiO2)1)。60mol% of nano -SiO2 powder with a purity of 99.95wt% was added with water and stirred to form colloidal silica, the mass ratio of water to SiO2 was 2:1, 12mol% of commercially available nickel fibers with a diameter of Spherical iron powder and 8mol% commercially available nickelous oxide with a purity of 98wt% are added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is evenly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body The green body of the block forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 20 MPa, and the temperature of the porous block is 900 ° C. The porosity of the obtained porous block is 15% by volume. The density is 1.2g/cm 3 , and the conductivity is 1.2Ω·cm. The porous block and the conductive cathode current collector are combined as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon environment, the temperature The temperature is 850°C, and the constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the silicon-metal nanowire composite material 52Si/48(Ni 18 Fe 17 (NiSi 2 ) 3 (FeSi 2 ) 4 (Fe 2 O 3 ) 5 (SiO 2 ) 1 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例7Example 7
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将6mol％的市售直径为1～5μm的镍纤维及14mol％市售的纯度为98wt％的氧化亚镍和30mol％直径为20～200nm，长度为5～10μm的碳纤维加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为20MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为27体积％，密度为0.8g／cm3，电导率为0.2Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaC12为电解质，在氩气的环境中，温度为800℃，用稳压器控制电压进行恒电压电解，槽电压为2.6V。经过22小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物纳米硅金属碳复合材料46Si／26(Ni18(NiSi)48iC3(SiO2)1)／28C。50mol% of nano -SiO2 powder with a purity of 99.95wt% was added with water and stirred to form colloidal silica, the mass ratio of water to SiO2 was 2:1, 6mol% of commercially available nickel fibers with a diameter of Commercially available nickel oxide with a purity of 98wt% and 30mol% carbon fibers with a diameter of 20-200nm and a length of 5-10μm are added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture , and then make the mixture into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 20 MPa, and the temperature of the porous block is 900 ° C. The obtained porous block The porosity of the block is 27% by volume, the density is 0.8g/cm 3 , and the electrical conductivity is 0.2Ω·cm. The porous block is combined with a conductive cathode current collector as the cathode, a graphite rod as the anode, and CaCl 2 as the Electrolyte, in the environment of argon gas, the temperature is 800 ℃, the constant voltage electrolysis is carried out with voltage stabilizer control voltage, cell voltage is 2.6V. After 22 hours of electrolysis, the electrolysis product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the product nano-silicon-metal-carbon composite material 46Si/26(Ni 18 (NiSi) 4 8iC 3 (SiO 2 ) 1 )/28C .
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例8Example 8
将55mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将5mol％的市售直径为2～5μm的类球形钛粉及10mol％市售的纯度为98wt％的二氧化钛和30mol％粒径为11～15μm的焦炭加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属、金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为10MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为30体积％，密度为1.3g／cm3，电导率为0.5Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.6V。经过11小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物纳米硅金属碳复合材料53Si53／19(Ti12(TiSi2)3SiC3(SiO2)1)／28C。所述复合材料中单质硅呈结晶状，单质硅呈颗粒状和线状，颗粒状单质硅的粒径小于100nm，线状单质硅的直径小于100nm。所述复合材料中碳呈球状或类球状。55mol% of nano- SiO2 powder with a purity of 99.95wt% was stirred with water to form colloidal silica, the mass ratio of water and SiO2 was 2:1, and 5mol% of commercially available spherical titanium powder with a diameter of 2 to 5 μm and Add 10mol% of commercially available titanium dioxide with a purity of 98wt% and 30mol% of coke with a particle size of 11-15μm into the colloid, and perform high-speed mechanical fusion so that the silica is evenly coated on the metal, metal oxide and carbon to form a mixture , and then make the mixture into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 10 MPa, and the temperature of the porous block is 900 ° C. The obtained porous block The porosity of the block is 30% by volume, the density is 1.3g/cm 3 , and the electrical conductivity is 0.5Ω·cm. The porous block is combined with a conductive cathode current collector as the cathode, a graphite rod as the anode, and CaCl 2 as the Electrolyte, in the environment of argon gas, the temperature is 900 ℃, the constant voltage electrolysis is carried out with voltage regulator control voltage, cell voltage is 2.6V. After 11 hours of electrolysis, the electrolysis product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the product nano-silicon-metal-carbon composite material 53Si 53 /19 (Ti 12 (TiSi 2 ) 3 SiC 3 (SiO 2 ) 1 ) /28C. The elemental silicon in the composite material is crystallized, the elemental silicon is granular and linear, the particle diameter of the granular elemental silicon is less than 100 nm, and the diameter of the linear elemental silicon is less than 100 nm. The carbon in the composite material is spherical or spherical.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例9Example 9
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将4mol％的市售直径为2～10μm的类球形镍粉和10mol％市售直径为2～10m的镍纤维及6mol％纯度为98wt％的氧化亚镍和30mol％的直径为20～200nm，长度为5～10μm的碳纤维加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属、金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为30MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为14体积％，密度为1.8g／cm3，电导率为0.3Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.6V。经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物纳米硅金属碳复合材料47Si/25(Ni17(NiSi)48iC2(SiO2)2)／28C。50mol% of nano- SiO2 powder with a purity of 99.95wt% is stirred with water to form colloidal silica, the mass ratio of water and SiO2 is 2:1, and 4mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm and 10mol% of commercially available nickel fibers with a diameter of 2 to 10m and 6mol% of nickel oxide with a purity of 98wt% and 30mol% of carbon fibers with a diameter of 20 to 200nm and a length of 5 to 10 μm are added to the colloid, and high-speed mechanical fusion is added. The silicon dioxide is uniformly coated on the metal, metal oxide and carbon to form a mixture, and then the mixture is made into a bulk green body, which forms a porous block under a certain mechanical pressure or a certain temperature, and the porous block system The forming mechanical pressure is 30MPa, and the temperature for making the porous block is 900°C. The porosity of the obtained porous block is 14 volume%, the density is 1.8g/cm 3 , and the electrical conductivity is 0.3Ω·cm. The cathode current collector composite is used as the cathode, the graphite rod is used as the anode, and CaCl2 is used as the electrolyte. In an argon environment, the temperature is 900 ° C, and the voltage is controlled by a voltage regulator for constant voltage electrolysis. The cell voltage is 2.6V. After 20 hours of electrolysis, the electrolysis product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the product nano-silicon-metal-carbon composite material 47Si/25(Ni 17 (NiSi) 4 8iC 2 (SiO 2 ) 2 )/28C .
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例10Example 10
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将2mol％的市售直径为2～10μm的类球形铝粉，10mol％市售直径为2～10μm的锡粉以及4mol％纯度为98wt％的氧化铝和30mol％的直径为20～200nm，长度为5～10μm的碳纤维加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属、金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为20MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为20体积％，密度为1.1g／cm3，电导率为0.3Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.6V。经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物纳米硅金属碳复合材料48Si／24(Al9Sn10SiC3(SiO2)2)／28C。50mol% of nano- SiO2 powder with a purity of 99.95wt% was added with water and stirred to form colloidal silica, the mass ratio of water to SiO2 was 2:1, and 2mol% of commercially available spherical aluminum powder with a diameter of 2 to 10 μm was added, 10mol% commercially available tin powder with a diameter of 2 to 10 μm, 4mol% of alumina with a purity of 98wt%, and 30mol% of carbon fibers with a diameter of 20 to 200nm and a length of 5 to 10μm are added to the colloid, and high-speed mechanical fusion is added to make Silica is uniformly coated on metal, metal oxide and carbon to form a mixture, and then the mixture is made into a block green body, which forms a porous block under a certain mechanical pressure or a certain temperature, and the porous block is made The mechanical pressure is 20MPa, and the temperature of the porous block is 900°C. The obtained porous block has a porosity of 20 volume%, a density of 1.1g/cm 3 , and an electrical conductivity of 0.3Ω·cm. The porous block and the conductive The cathode current collector is composited as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon environment, the temperature is 900 ° C, and the voltage is controlled by a voltage regulator for constant voltage electrolysis. The cell voltage is 2.6V. After 20 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the product nano-silicon-metal-carbon composite material 48Si/24(Al 9 Sn 10 SiC 3 (SiO 2 ) 2 )/28C.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例11Example 11
将50mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将10mol％市售直径为2～10μm的锡粉以及5mol％纯度为98wt％的二氧化钛和35mol％的粒径为3～6μm的石墨片加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属、金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为15MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为18体积％，密度为1.4g／cm3，电导率为0.2Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.7V。经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到产物纳米硅金属碳复合材料48Si／81(Ti4Sn10(TiSi2)1SiC2(SiO2)2)／33C。Add 50mol% of nano -SiO2 powder with a purity of 99.95wt% to water and stir to form colloidal silica. The mass ratio of water to SiO2 is 2:1, and 10mol% of commercially available tin powder with a diameter of 98wt% of titanium dioxide and 35mol% of graphite flakes with a particle size of 3 to 6 μm are added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal, metal oxide and carbon to form a mixture, and then the mixture The block green body is made into a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 15 MPa, and the temperature of the porous block is 900 ° C. The pores of the obtained porous block The ratio is 18% by volume, the density is 1.4g/cm 3 , and the conductivity is 0.2Ω·cm. The porous block and the conductive cathode current collector are combined as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In the air environment, the temperature is 900°C, the constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.7V. After 20 hours of electrolysis, the electrolysis product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the product nano-silicon-metal-carbon composite material 48Si/81(Ti 4 Sn 10 (TiSi 2 ) 1 SiC 2 (SiO 2 ) 2 )/33C.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例12Example 12
将20mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将10mol％市售直径为2～10μm的市售直径为2～10μm的类球形镍粉以及5mol％纯度为98wt％的二氧化钛和65mol％的粒径为3～6μm的石墨片加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属、金属氧化物和碳上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为25MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为10体积％，密度为1.9g／cm3，电导率为0.1Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.7V3经过20小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到硅金属碳纳米线复合材料17Si／20(Ti4Ni8(TiSi)1(NiSi)28iC3(SiO2)2)／63C。Add 20mol% of nano- SiO2 powder with a purity of 99.95wt% to water and stir to form colloidal silica. 10μm quasi-spherical nickel powder, 5mol% titanium dioxide with a purity of 98wt%, and 65mol% graphite flakes with a particle size of 3-6μm are added to the colloid, and high-speed mechanical fusion is carried out so that the silicon dioxide is uniformly coated on the metal and metal oxide. A mixture is formed on the material and carbon, and then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 25MPa, and the temperature of the porous block is At 900°C, the porosity of the obtained porous block is 10% by volume, the density is 1.9g/cm 3 , and the electrical conductivity is 0.1Ω·cm. The porous block is combined with a conductive cathode current collector as the cathode, and a graphite rod is used as the cathode. The anode uses CaCl 2 as the electrolyte, in an argon environment, the temperature is 900°C, and the voltage is controlled by a voltage regulator for constant voltage electrolysis. The cell voltage is 2.7V. After 20 hours of electrolysis, the electrolyzed products are sequentially washed with water and absolute ethanol Rinse, vacuum dry, and sieve to obtain the silicon metal carbon nanowire composite material 17Si/20(Ti 4 Ni 8 (TiSi) 1 (NiSi) 2 8iC 3 (SiO 2 ) 2 )/63C.
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例13Example 13
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉和20mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为30MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为10体积％，密度为1.6g／cm3，电导率为2.1Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过10小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料50Si／50(Ni35(NiSi)9(SiO2)6)。60mol% of nano- SiO2 powder with a purity of 99.95wt% was stirred with water to form colloidal silica, the mass ratio of water and SiO2 was 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm and 20mol% of commercially available nickel oxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body. The billet forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 30MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 10% by volume and the density is 1.6g. /cm 3 , the conductivity is 2.1Ω·cm, the composite porous block and the conductive cathode current collector are used as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon atmosphere, the temperature is 850°C. The constant voltage electrolysis is carried out by controlling the voltage with a voltage stabilizer, and the cell voltage is 2.5V. After 10 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain a nickel powder-supported nano-silicon particle composite material 50Si/50(Ni 35 (NiSi) 9 (SiO 2 ) 6 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例14Example 14
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉和20mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为25MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为15体积％，密度为1.55g／cm3，电导率为1.7Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过9.2小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料51Si／49(Ni35(NiSi)9(SiO2)5)。60mol% of nano- SiO2 powder with a purity of 99.95wt% was stirred with water to form colloidal silica, the mass ratio of water and SiO2 was 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm and 20mol% of commercially available nickel oxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body. The billet forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 25MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 15% by volume and the density is 1.55g. /cm 3 , the conductivity is 1.7Ω·cm, the porous block is combined with the conductive cathode current collector as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon environment, the temperature is 850°C. The constant voltage electrolysis is carried out by controlling the voltage with a voltage stabilizer, and the cell voltage is 2.5V. After 9.2 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain a nickel powder-supported nano-silicon particle composite material 51Si/49(Ni 35 (NiSi) 9 (SiO 2 ) 5 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例15Example 15
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉和20mol％市售的纯度为98wt％的氧化亚镍加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为20MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为20体积％，密度为1.5g／cm3，电导率为1.4Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为850℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过8小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料52Si／48(Ni35(NiSi)9(SiO2)4)。60mol% of nano- SiO2 powder with a purity of 99.95wt% was stirred with water to form colloidal silica, the mass ratio of water and SiO2 was 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm and 20mol% of commercially available nickel oxide with a purity of 98wt% is added to the colloid, and high-speed mechanical fusion is performed so that the silicon dioxide is uniformly coated on the metal nickel to form a mixture, and then the mixture is made into a block green body. The billet forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 20MPa, and the temperature of the porous block is 900°C. The porosity of the obtained porous block is 20% by volume and the density is 1.5g. /cm 3 , the conductivity is 1.4Ω·cm, the porous block is combined with the conductive cathode current collector as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. In an argon atmosphere, the temperature is 850°C. The constant voltage electrolysis is carried out by controlling the voltage with a voltage stabilizer, and the cell voltage is 2.5V. After 8 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the nickel powder-loaded nano-silicon particle composite material 52Si/48(Ni 35 (NiSi) 9 (SiO 2 ) 4 ).
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例16Example 16
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉，10mol％市售的纯度为98wt％的氧化亚镍和10mol％市售的球形石墨负极材料BTR-918加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为15MPa，多孔块体制成温度为900℃，得到的多孔块体的孔隙率为22体积％，密度为1.43g／cm3，电导率为1.4Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为950℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过7.5小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料53Si／37(Ni25(NiSi)9(SiO2)3)10C。其实施例16在950℃下制备硅基金属碳纳米线复合材料的扫描电子显微镜图像如图2所示。60mol% of nano- SiO2 powder with a purity of 99.95wt% is stirred with water to form colloidal silica, the mass ratio of water and SiO2 is 2:1, and 20mol% of commercially available spherical nickel powder with a diameter of 2 to 10 μm, 10mol% of commercially available nickel oxide with a purity of 98wt% and 10mol% of commercially available spherical graphite negative electrode material BTR-918 are added to the colloid, and high-speed mechanical fusion is performed so that silicon dioxide is evenly coated on the metal nickel to form a mixture. Then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 15 MPa, and the temperature of the porous block is 900 ° C. The obtained porous block The porosity of the body is 22 volume%, the density is 1.43g/cm 3 , and the conductivity is 1.4Ω·cm. The porous block is combined with a conductive cathode current collector as the cathode, the graphite rod is used as the anode, and CaCl 2 is used as the electrolyte. , in the environment of argon gas, the temperature is 950°C, the constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.5V. After 7.5 hours of electrolysis, the electrolyzed product was washed with water and absolute ethanol in sequence, dried in vacuum, and sieved to obtain the nickel powder-supported nano-silicon particle composite material 53Si/37(Ni 25 (NiSi) 9 (SiO 2 ) 3 ) 10C. The scanning electron microscope image of the silicon-based metal-carbon nanowire composite material prepared at 950° C. in Example 16 is shown in FIG. 2 .
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
实施例17Example 17
将60mol％的纯度为99.95wt％的纳米SiO2粉末加水搅拌形成二氧化硅胶体，水与SiO2的质量比为2：1，将20mol％的市售直径为2～10μm的类球状镍粉、19mol％市售的纯度为98wt％的氧化亚镍和1mol％市售的纯度为99wt％的氧化钙加入胶体中，加以高速机械溶合，使得二氧化硅均匀包覆在金属镍上形成混合物，再将混合物制成块体生坯，块体生坯在一定的机械压力或一定温度下形成多孔块体，多孔块体制成机械压力为20MPa，多孔块体制成温度为1000℃，得到的多孔块体的孔隙率为13体积％，密度为1.56g／cm3，电导率为2.9Ω·cm，将多孔块体与导电的阴极集流体复合作为阴极，以石墨棒作为阳极，以CaCl2为电解质，在氩气的环境中，温度为900℃，用稳压器控制电压进行恒电压电解，槽电压为2.5V。经过11小时电解后将电解产物依次用水和无水乙醇冲洗，真空干燥，过筛后得到镍粉负载纳米硅颗粒复合材料50Si／50(Ni35(NiSi)8(CaSi)(SiO2)6)。It is 99.95wt% nano- SiO2 powder that is 99.95wt% by 60mol% purity and is stirred with water to form silica colloid, and the mass ratio of water and SiO2 is 2:1, and 20mol% of the commercially available diameter is the quasi-spherical nickel powder of 2～10 μm, 19mol% commercially available purity of 98wt% nickel oxide and 1mol% commercially available calcium oxide of 99wt% purity are added to the colloid, and high-speed mechanical fusion is performed so that silicon dioxide is uniformly coated on the metal nickel to form a mixture. Then the mixture is made into a block green body. The block green body forms a porous block under a certain mechanical pressure or a certain temperature. The mechanical pressure of the porous block is 20 MPa, and the temperature of the porous block is 1000 ° C. The obtained porous block The porosity of the body is 13% by volume, the density is 1.56g/cm 3 , and the electrical conductivity is 2.9Ω·cm. The porous block is combined with a conductive cathode current collector as the cathode, a graphite rod as the anode, and CaCl 2 as the electrolyte. , in the environment of argon gas, the temperature is 900°C, the constant voltage electrolysis is carried out by controlling the voltage with a voltage regulator, and the cell voltage is 2.5V. After 11 hours of electrolysis, the electrolysis product was washed with water and ethanol in sequence, dried in vacuum, and sieved to obtain the nickel powder-loaded nano-silicon particle composite material 50Si/50(Ni 35 (NiSi) 8 (CaSi)(SiO 2 ) 6 ) .
所得复合材料按照与实施例1相同的方法制备电极，进行电化学性能测试，其测试电化学性能如表1所示。The obtained composite material was prepared by the same method as in Example 1 to prepare an electrode, and the electrochemical performance test was performed, and the tested electrochemical performance is shown in Table 1.
将实施例的电化学性能测试结果进行对比，结果如表1所示。对比测试结果，对于相同的控制电解条件下，原料中SiO2含量多的样品其首次嵌锂容量较高，但首次库伦效率会较低。The electrochemical performance test results of the examples were compared, and the results are shown in Table 1. Comparing the test results, under the same controlled electrolysis conditions, the sample with more SiO2 content in the raw material has a higher initial lithium intercalation capacity, but the initial Coulombic efficiency will be lower.
表1纳米硅碳复合材料的电化学性能Table 1 Electrochemical properties of nano-silicon-carbon composites
Claims (23)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310538238.5A CN104617278B (en) | 2013-11-04 | 2013-11-04 | A kind of nano-silicon-metal composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310538238.5A CN104617278B (en) | 2013-11-04 | 2013-11-04 | A kind of nano-silicon-metal composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104617278A true CN104617278A (en) | 2015-05-13 |
| CN104617278B CN104617278B (en) | 2017-01-25 |
Family
ID=53151630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310538238.5A Active CN104617278B (en) | 2013-11-04 | 2013-11-04 | A kind of nano-silicon-metal composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104617278B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900843A (en) * | 2015-06-13 | 2015-09-09 | 田东 | Preparation method of silicon carbon composite anode material |
| CN107546387A (en) * | 2017-08-10 | 2018-01-05 | 北京工业大学 | A kind of molten-salt electrolysis prepares vermiform germanium base nano-wire and application |
| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A metal-coated porous silicon composite electrode material and its preparation method |
| CN108011093A (en) * | 2016-10-31 | 2018-05-08 | 捷恩智株式会社 | Lithium occlusion releasable material, electrode, the manufacture method of lithium rechargeable battery and lithium occlusion releasable material |
| WO2018113267A1 (en) * | 2016-12-21 | 2018-06-28 | 宁德时代新能源科技股份有限公司 | Negative electrode material for lithium ion battery and preparation method therefor |
| CN108335800A (en) * | 2017-12-29 | 2018-07-27 | 天津工业大学 | Copper silicon integrated electrode and preparation method thereof |
| CN109671905A (en) * | 2017-10-13 | 2019-04-23 | 现代自动车株式会社 | Anode and preparation method thereof for all-solid-state battery |
| CN109713286A (en) * | 2018-12-29 | 2019-05-03 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery |
| CN109768263A (en) * | 2019-03-01 | 2019-05-17 | 江苏赛清科技有限公司 | A kind of lithium battery high capacity composite negative pole material and preparation method thereof |
| CN110079835A (en) * | 2019-04-15 | 2019-08-02 | 昆明理工大学 | A kind of SiO2/VO2The method that mixture direct electrodeoxidation prepares lithium ion battery silicon vanadium negative electrode material |
| CN110556535A (en) * | 2019-09-17 | 2019-12-10 | 上海理工大学 | Preparation method of flexible three-dimensional metal lithium negative electrode material |
| CN110993910A (en) * | 2019-11-29 | 2020-04-10 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon carbon composite material and preparation method thereof |
| CN108598412B (en) * | 2018-04-23 | 2020-06-16 | 中南大学 | Metal-organic-based silicon alloy composite anode material and preparation method thereof |
| CN112219296A (en) * | 2018-01-19 | 2021-01-12 | 安普瑞斯股份有限公司 | Stable Prelithiated Silica Particles for Lithium Ion Battery Anodes |
| CN112335075A (en) * | 2018-05-25 | 2021-02-05 | 美国纳米有限责任公司 | Silica fiber-incorporated battery |
| CN113991099A (en) * | 2021-10-27 | 2022-01-28 | 昆明理工大学 | A method for preparing nano-silicon-based negative electrode material from silicon cutting waste |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101271974A (en) * | 2007-03-22 | 2008-09-24 | 中信国安盟固利新能源科技有限公司 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
| JP4883323B2 (en) * | 2008-08-26 | 2012-02-22 | 信越化学工業株式会社 | Non-aqueous electrolyte secondary battery negative electrode material, Si-O-Al composite manufacturing method, non-aqueous electrolyte secondary battery negative electrode and non-aqueous electrolyte secondary battery |
| JP2013008586A (en) * | 2011-06-24 | 2013-01-10 | Sony Corp | Lithium ion secondary battery, negative electrode for lithium ion secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device |
| CN103107315B (en) * | 2011-11-10 | 2016-03-30 | 北京有色金属研究总院 | A kind of nano-silicone wire/carbon composite material and preparation method thereof |
| US20130202967A1 (en) * | 2012-02-07 | 2013-08-08 | Jae-Hyuk Kim | Negative active material for rechargeable lithium battery and rechargeable lithium battery including same |
-
2013
- 2013-11-04 CN CN201310538238.5A patent/CN104617278B/en active Active
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900843A (en) * | 2015-06-13 | 2015-09-09 | 田东 | Preparation method of silicon carbon composite anode material |
| CN108011093A (en) * | 2016-10-31 | 2018-05-08 | 捷恩智株式会社 | Lithium occlusion releasable material, electrode, the manufacture method of lithium rechargeable battery and lithium occlusion releasable material |
| WO2018113267A1 (en) * | 2016-12-21 | 2018-06-28 | 宁德时代新能源科技股份有限公司 | Negative electrode material for lithium ion battery and preparation method therefor |
| CN107546387B (en) * | 2017-08-10 | 2019-12-03 | 北京工业大学 | A kind of molten-salt electrolysis prepares vermiform germanium base nano-wire and application |
| CN107546387A (en) * | 2017-08-10 | 2018-01-05 | 北京工业大学 | A kind of molten-salt electrolysis prepares vermiform germanium base nano-wire and application |
| CN109671905A (en) * | 2017-10-13 | 2019-04-23 | 现代自动车株式会社 | Anode and preparation method thereof for all-solid-state battery |
| CN109671905B (en) * | 2017-10-13 | 2021-08-17 | 现代自动车株式会社 | Anode for all-solid-state battery and method of making the same |
| CN107623121A (en) * | 2017-10-18 | 2018-01-23 | 山东大学 | A metal-coated porous silicon composite electrode material and its preparation method |
| CN107623121B (en) * | 2017-10-18 | 2019-12-27 | 山东大学 | Metal-coated porous silicon composite electrode material and preparation method thereof |
| CN108335800A (en) * | 2017-12-29 | 2018-07-27 | 天津工业大学 | Copper silicon integrated electrode and preparation method thereof |
| EP3740986A4 (en) * | 2018-01-19 | 2021-09-22 | Amprius, Inc. | STABILIZED, PRE-LITHIUM SILICON OXIDE PARTICLES FOR ANODES OF LITHIUM-ION BATTERIES |
| CN112219296A (en) * | 2018-01-19 | 2021-01-12 | 安普瑞斯股份有限公司 | Stable Prelithiated Silica Particles for Lithium Ion Battery Anodes |
| US11152613B2 (en) | 2018-01-19 | 2021-10-19 | Amprius, Inc. | Stabilized, prelithiated silicon oxide particles for lithium ion battery anodes |
| US11784307B2 (en) | 2018-01-19 | 2023-10-10 | Amprius Technologies, Inc. | Stabilized, prelithiated silicon oxide particles for lithium ion battery anodes |
| CN108598412B (en) * | 2018-04-23 | 2020-06-16 | 中南大学 | Metal-organic-based silicon alloy composite anode material and preparation method thereof |
| CN112335075A (en) * | 2018-05-25 | 2021-02-05 | 美国纳米有限责任公司 | Silica fiber-incorporated battery |
| CN109713286B (en) * | 2018-12-29 | 2020-07-24 | 安普瑞斯（南京）有限公司 | Silicon-based composite material for lithium ion secondary battery and preparation method thereof |
| CN109713286A (en) * | 2018-12-29 | 2019-05-03 | 安普瑞斯（南京）有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion secondary battery |
| CN109768263A (en) * | 2019-03-01 | 2019-05-17 | 江苏赛清科技有限公司 | A kind of lithium battery high capacity composite negative pole material and preparation method thereof |
| CN110079835A (en) * | 2019-04-15 | 2019-08-02 | 昆明理工大学 | A kind of SiO2/VO2The method that mixture direct electrodeoxidation prepares lithium ion battery silicon vanadium negative electrode material |
| CN110556535A (en) * | 2019-09-17 | 2019-12-10 | 上海理工大学 | Preparation method of flexible three-dimensional metal lithium negative electrode material |
| CN110993910A (en) * | 2019-11-29 | 2020-04-10 | 国联汽车动力电池研究院有限责任公司 | A kind of silicon carbon composite material and preparation method thereof |
| CN113991099A (en) * | 2021-10-27 | 2022-01-28 | 昆明理工大学 | A method for preparing nano-silicon-based negative electrode material from silicon cutting waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104617278B (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104617278B (en) | A kind of nano-silicon-metal composite material and preparation method thereof | |
| Zhao et al. | A review on anode for lithium-sulfur batteries: Progress and prospects | |
| Jin et al. | 3D lithium metal embedded within lithiophilic porous matrix for stable lithium metal batteries | |
| Gao et al. | Self-supporting N, P doped Si/CNTs/CNFs composites with fiber network for high-performance lithium-ion batteries | |
| JP5826405B2 (en) | Nanosilicon carbon composite material and method for preparing the same | |
| Ji et al. | Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries | |
| EP2919298B1 (en) | Si/C composite anodes for lithium-ion batteries with a sustained high capacity per unit area | |
| US20110163274A1 (en) | Electrode composite, battery electrode formed from said composite, and lithium battery comprising such an electrode | |
| JP2019505948A (en) | Composite silicon negative electrode material, preparation method and use | |
| Li et al. | Silicon anodes for high‐performance storage devices: structural design, material compounding, advances in electrolytes and binders | |
| CN106384825A (en) | Silicon carbon composite microsphere, and preparation method and application thereof | |
| CN106784833A (en) | Silicon-carbon cathode material and preparation method thereof | |
| CN105609749A (en) | Silicon nanowire and application thereof | |
| WO2021212392A1 (en) | Three-dimensional composite metal lithium negative electrode, metal lithium battery and apparatus | |
| CN113054177B (en) | A kind of multi-component composite silicon-based negative electrode and its preparation method and application | |
| CN106784698A (en) | Si/SiC/C composites and preparation method and lithium ion battery negative and battery | |
| CN108306009A (en) | A kind of silicon-carbon oxide composite negative pole material, preparation method and lithium ion battery | |
| CN107464923A (en) | A kind of compound high-capacity lithium ion cell material of nano zine oxide/porous carbon in situ and preparation method thereof | |
| CN105393386A (en) | Composite particles, method for manufacturing same, electrode, and non-aqueous electrolyte secondary cell | |
| KR20150117172A (en) | Negative electrode active material, methode for synthesis the same, and lithium rechargable battery including the same | |
| CN108630917A (en) | Si @ C @ fibrous carbon @ C composite material and preparation method and application thereof | |
| Xie et al. | Large-size carbon-coated SnO 2 composite as improved anode material for lithium ion batteries | |
| CN106531995B (en) | A kind of graphene-loaded nanometer magnesium sulfide composite material and preparation method thereof | |
| Wang et al. | A mini review: Nanostructured silicon-based materials for lithium ion battery | |
| Sun et al. | MWCNT/Cellulose collector as scaffold of nano-silicon for Li-Si battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160322 Address after: 101407 Beijing Yanqi Yanqi Economic Development Zone Huairou District Road No. 3 Applicant after: GUOLIAN AUTOMOBILE POWER CELL INSTITUTE CO., LTD. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Applicant before: General Research Institute for Nonferrous Metals |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |