CN104617278B - Nano silicon metal composite material and preparation method thereof - Google Patents
Nano silicon metal composite material and preparation method thereof Download PDFInfo
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- CN104617278B CN104617278B CN201310538238.5A CN201310538238A CN104617278B CN 104617278 B CN104617278 B CN 104617278B CN 201310538238 A CN201310538238 A CN 201310538238A CN 104617278 B CN104617278 B CN 104617278B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 106
- 239000002905 metal composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 263
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 124
- 229910052751 metal Inorganic materials 0.000 claims abstract description 89
- 239000002184 metal Substances 0.000 claims abstract description 87
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 85
- 239000010703 silicon Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000126 substance Substances 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000001110 calcium chloride Substances 0.000 claims abstract description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 110
- 235000012239 silicon dioxide Nutrition 0.000 claims description 102
- 239000000203 mixture Substances 0.000 claims description 53
- 239000000084 colloidal system Substances 0.000 claims description 50
- 239000002131 composite material Substances 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 34
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 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
- 238000011065 in-situ storage Methods 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
- 229910052719 titanium Inorganic materials 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 5
- 235000011148 calcium chloride Nutrition 0.000 abstract 2
- 238000005868 electrolysis reaction Methods 0.000 description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 53
- 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 23
- 230000004927 fusion Effects 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 229910052744 lithium Inorganic materials 0.000 description 21
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000011056 performance test Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 16
- 229910005883 NiSi Inorganic materials 0.000 description 12
- 238000009830 intercalation Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000002687 intercalation Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002210 silicon-based material Substances 0.000 description 9
- 239000002070 nanowire Substances 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 229910021332 silicide Inorganic materials 0.000 description 7
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229910012990 NiSi2 Inorganic materials 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- -1 silicon oxide compound Chemical class 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910005331 FeSi2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910008479 TiSi2 Inorganic materials 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
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021334 nickel silicide Inorganic materials 0.000 description 2
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 2
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000007740 vapor deposition Methods 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
- 229910004709 CaSi Inorganic materials 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
- 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
- 229910008484 TiSi Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 229910052786 argon Inorganic materials 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
- 239000011230 binding agent Substances 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 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
- 239000003054 catalyst 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
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 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
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 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
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000005406 washing 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
A nano silicon metal composite used for a negative electrode of a lithium ion battery comprises the following parts: (a) the first component part is simple substance silicon with the content accounting for 5-75mol% of the nano silicon metal composite; (b) the second component part contains a metal element, a compound formed and a silicon oxygen compound formed by the metal element and silicon, the second component part content accounts for 25 to 95mol% of the nano silicon metal composite; and (c) the third component part is simple substance carbon with the content accounting for 0-70mol% of the nano silicon metal composite. The preparation method is as follows: a porous block, comprising silica and metal or metal oxide and the like, and a conductive negative electrode current collector are compounded as a negative electrode, graphite or an inert positive electrode is used as a positive electrode, the negative electrode and the positive electrode are placed in a mixed salt melt electrolyte using CaCl2 or CaCl2 as the main components, voltage is applied between the negative electrode and the positive electrode, current density and electrolytic quantity are controlled, silica in the porous block is electrolyzed and reduced into nano silicon, and a nano silicon metal composite material is prepared on the negative electrode.
Description
Technical Field
The invention relates to a silicon metal composite material for a lithium ion battery and a preparation method thereof.
Background
Lithium ion secondary batteries are widely used in various electronic devices. As the demand for and performance of electronic devices for their power system-chemical power source-grows dramatically, most commercial lithium ion batteries have anodes comprising materials such as graphite that incorporate lithium via an intercalation mechanism upon charging. Such an insertion-type anode exhibits better cycle life and coulombic efficiency, but is limited by a lower theoretical capacity (372 mAh/g) and it is difficult to improve the performance of the battery through a battery preparation process.
The second anode material such as Si, Sn and Sb, which introduces lithium through an alloying mechanism during charging, is a better choice of high-capacity anode materials, wherein silicon has the advantages of more than 10 times of theoretical electrochemical capacity (4200 mAh/g) compared with widely used carbon materials, low lithium intercalation voltage (lower than 0.5V), no co-intercalation of solvent molecules in the intercalation process, abundant content in earth crust and the like. However, the silicon material as an anode shows relatively poor cycle life and coulombic efficiency, and the main reasons are that the silicon material has poor conductivity, and the generated internal stress causes the damage of the material structure in the severe volume effect (volume change rate: 280% -310%) generated in the electrochemical lithium-releasing process, so that the separation of electrode materials, electrode materials and conductive agents (such as carbon), adhesives and electrode materials and current collectors is caused, and further the electrical contact is lost, and the cycle performance of the electrode is reduced rapidly.
There are two main solutions proposed to solve this problem: one of the methods is to make silicon into a nano-scale. Because the volume change of silicon can be reduced to some extent with the reduction of particles, the internal stress of the electrode is reduced. However, the nano material is easy to agglomerate in the circulation process, which is not enough to improve the performance of the battery to be practical. Secondly, the method adopts the compounding of materials such as silicon and metal, namely the compounding of nano silicon with electrochemical activity and metal materials with good conductivity. On one hand, the metal material can improve the conductivity of the silicon material, so that all silicon plays a role of an active material in electrochemical lithium desorption, and on the other hand, the metal material can be used as a buffer framework to disperse and buffer internal stress generated by volume change of the silicon material in the lithium desorption process, so that the silicon metal composite material has good cycle performance.
Wang G.X. et al (J.Power. sources, 2000, 88: 278-. Kang kibum et al (chem.Sci., 2011, 2: 1090) grow a silicon-nickel nanowire array on a nickel substrate, silicon is deposited on the outer layer through a vapor deposition method and used for a lithium ion battery cathode material, the inner layer silicon-nickel nanowire is used as a framework, the outer layer silicon is used as an active material, the volume effect of the silicon material in the lithium desorption and intercalation process is restrained to a certain extent, meanwhile, the conductivity of the silicon material is improved, and the good cycle performance is kept. ZhangShichao et al (adv. Mater.2010, 22: 5378-. These studies indicate that nano silicon metal composites are generally formed by compounding metal and silicon or silicon alloy and silicon, and the silicon metal can be physically or chemically bonded. The physical combination does not help greatly to improve the cycle performance of the silicon material, and preferably, the silicon and the metal form chemical combination, so that the volume effect of the silicon material can be effectively improved, and the material with stable cycle performance is obtained. The main methods for preparing the silicon metal composite materials at present comprise a chemical vapor deposition method, a thermal vapor deposition method, a high-energy ball milling method and the like. These methods of preparation involve complicated processes (e.g., templating), difficult control of the processes, expensive equipment (e.g., chemical vapor deposition), and difficult mass production.
Disclosure of Invention
The invention aims to overcome the defect that the cycle stability of the existing nano silicon metal composite material is poor due to the separation of silicon and metal in the process of lithium intercalation and deintercalation when the silicon and the metal are used as a negative electrode material of a lithium ion battery because of physical combination, and provides the nano silicon metal composite material with good cycle stability. A small amount of silicon metal alloy can limit the volume change of the nano silicon metal composite material in the process of lithium intercalation and deintercalation, so that silicon and metal in the nano silicon metal composite material can not be separated from each other due to the increase of cycle times, and the cycle stability of the nano silicon metal composite material is improved. The invention also provides a preparation method of the nano silicon metal composite material, which has the advantages of short production flow, no pollution, simple operation, easily obtained raw materials, cheap equipment and easy continuous production.
The invention adopts the following technical scheme:
the invention provides a nano-silicon metal composite material for a lithium ion battery, which at least contains simple substance silicon and a second componentThe alloy comprises transition metal elements, elements such as aluminum, tin, antimony and the like, alkaline earth elements, carbon and oxygen, and the molar percentage of each component is as follows: 5-75 mol% of simple substance silicon, 25-95 mol% of a second component, wherein the second component comprises transition metal, or a combination thereof, or an intermetallic compound formed by the transition metal and the silicon, aluminum, tin, antimony, or a combination thereof, or an intermetallic compound formed by the transition metal and the silicon, alkaline earth metal, carbon, oxygen, or a compound element of the carbon, the oxygen and the silicon, and 0-70 mol% of simple substance carbon. Wherein the molar percentage of the simple substance silicon is further preferably 10-55 mol%. In addition, the material can also contain a silicon oxide compound SiOxX is more than 0 and less than or equal to 2, and the mol percentage of the SiO is 0.1-5 mol percentx. The mole percentage is relative to the nano silicon metal composite material for the lithium ion battery.
The simple substance silicon in the nano silicon metal composite material for the lithium ion battery is one or more of linear, granular, tubular and flaky; the metal is one or more of spherical, quasi-spherical, linear, flaky and reticular; the simple substance carbon is one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape. Wherein the simple substance silicon is at least one of a nano silicon wire, a nano silicon particle, a nano silicon tube or a nano silicon chip. The particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm.
The invention provides a preparation method of a nano silicon metal composite material, which comprises the following specific steps: the porous block composed of silicon dioxide and metal material is compounded with conductive cathode current collector to be used as cathode, graphite or inert anode is used as anode, and placed in CaCl2Or with CaCl2In the mixed salt melt electrolyte which is mainly used, voltage is applied between a cathode and an anode, the electrolysis time is controlled, so that the silicon dioxide in the porous block is electrolyzed and reduced into the nano silicon, and the nano silicon metal composite material is prepared at the cathode.
The particle size of the silicon dioxide is 10nm to 1 mu m.
The porous block body composed of the silicon dioxide and the metal is prepared by firstly preparing silicon dioxide powder into a silicon dioxide colloid, wherein the mass ratio of the silicon dioxide to water is 20-50 wt% and 50-80 wt% when the colloid is prepared. Adding metal into a silicon dioxide colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on the metal to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 10-200 MPa and the temperature of 800-1400 ℃, wherein the porosity of the obtained porous block is 1-40% by volume, the porosity of the porous block is further preferably 10-30% by volume, and the density is 0.5-2.0 g/cm3Resistivity of 0.1-2. omega. cm
The porous block body composed of the silicon dioxide and the metal oxide is prepared by firstly preparing silicon dioxide powder into a silicon dioxide colloid, adding the metal oxide into the silicon dioxide colloid, carrying out high-speed mechanical fusion to enable the silicon dioxide to be uniformly coated on the metal oxide to form a mixture, then preparing the mixture into a block green body, forming the porous block body by the block green body at a certain mechanical pressure or a certain temperature, preparing the porous block body at a mechanical pressure of 10-200 MPa, preparing the porous block body at a temperature of 800-1400 ℃, wherein the porosity of the obtained porous block body is 1-40 volume percent, and the porosity of the porous block body is further preferably 10-30 volume percent.
The porous block body composed of the silicon dioxide, the metal and the carbon is characterized in that silicon dioxide powder is firstly prepared into a silicon dioxide colloid, the carbon and the metal are added into the silicon dioxide colloid, high-speed mechanical fusion is carried out, the silicon dioxide is uniformly coated on the metal and the carbon to form a mixture, then the mixture is prepared into a block body green body, the block body green body forms the porous block body under a certain mechanical pressure or a certain temperature, the porous block body is prepared into the porous block body under the mechanical pressure of 10-200 MPa, the porous block body is prepared into the temperature of 800-1400 ℃, the porosity of the obtained porous block body is 1-40%, and the porosity of the porous block body is further preferably 10-30.
The porous block body composed of silicon dioxide, metal oxide and carbon is characterized in that silicon dioxide powder is firstly prepared into silicon dioxide colloid, carbon and the metal oxide are added into the silicon dioxide colloid, high-speed mechanical fusion is carried out, so that the silicon dioxide is uniformly coated on the metal oxide and the carbon to form a mixture, then the mixture is prepared into a block body green body, the block body green body forms the porous block body under a certain mechanical pressure or a certain temperature, the porous block body is prepared into the porous block body with the mechanical pressure of 10-200 MPa and the porous block body preparation temperature of 800-1400 ℃, the porosity of the obtained porous block body is 1-40 volume percent, and the porosity of the porous block body is further preferably 10-30 volume percent.
The catalyst is prepared from CaCl2The main mixed salt melt electrolyte is CaCl2+MY1Wherein M is Ba, Li, Al, Cs, Na, K, Mg, Rb, Be or Sr, Y1Is Cl or F.
The voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis time is equal to or more than the electric quantity required by the theory when the electrolysis electric quantity reaches. The theoretical decomposition voltage is the theoretical calculated decomposition voltage of SiO2 in molten salt, which varies with molten salt composition and temperature. The theoretically required electric quantity is the electric quantity calculated according to the electrons consumed by SiO2 to become simple substance Si, and the electric quantity changes along with the change of the content of SiO 2.
The electrolysis is carried out at a temperature of 500 ℃ and 1000 ℃.
The invention provides a lithium ion battery which comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises the nano silicon metal composite material.
The invention has the following characteristics:
(1) the silicon metal ratio in the nano silicon metal composite material can be adjusted by adjusting the ratio of the raw material silicon dioxide and the metal, and the lithium insertion capacity, namely the specific capacity, of the nano silicon metal composite material can be adjusted;
(2) the content of silicon alloy and silicon oxide in the electrolytic product nano silicon metal composite material can be adjusted by controlling the electrolytic electric quantity, and the metallurgical bonding degree between silicon and metal is controlled, so that the electrochemical cycle stability of the nano silicon metal composite material is improved;
(3) the used raw materials have rich sources and low prices, and the raw materials and the preparation process have no pollution to the environment;
(4) the process is simple, the operation is simple and convenient, and the equipment is simple;
(5) the raw materials and the products are added or removed in a solid form, and the continuous production is easy to realize.
Drawings
FIG. 1 is a scanning electron microscope image of example 1, which uses a mixture of nickel powder, nickel protoxide and silicon dioxide as raw materials to prepare a nano silicon-based metal composite material at 900 ℃.
FIG. 2 is a scanning electron microscope image of the silicon-based metal carbon nanowire composite material prepared by the present invention at 950 ℃ in example 16 using a mixture of spherical carbon, nickel powder, nickel protoxide and silica as raw materials.
FIG. 3 is the X-ray diffraction pattern of the nano-silicon metal composite prepared by the invention at 900 ℃ in example 2.
Detailed Description
The invention will be further described with reference to the figures and examples. The description is intended to be illustrative of the invention and is not to be construed as limiting the invention.
The invention provides a nano silicon metal composite material for a lithium ion battery, which at least contains simple substance silicon and metal. The simple substance silicon in the material is obtained by electrolyzing silicon dioxide in raw materials through molten salt by an electrochemical method, the metal is obtained by metal in the raw materials and electrolyzing metal oxide, and the simple substance carbon is obtained by simple substance carbon in the raw materials. Therefore, the ratio of the simple substance silicon to the metal or the carbon in the nano silicon metal composite material can be adjusted by adjusting the ratio of the silicon dioxide, the metal and the metal oxide to the carbon in the raw materials. The lithium intercalation capacity of the nano silicon metal composite material can be adjusted by adjusting the proportion of the simple substance silicon, the metal and the carbon in the material. The silicon content is too low, the specific capacity of the nano silicon metal composite material is too low, and the requirement of the battery can not be met. The ratio of silicon is too high, and under the same other conditions, the specific capacity of the nano silicon metal composite material is higher, but the volume change of silicon caused by lithium intercalation and deintercalation is more severe because partial simple substance silicon cannot form effective combination with metal, so that the cycle performance of a battery using the nano silicon metal composite material is poorer. Thus, the nano-silicon metal composite has a molar percentage of elemental silicon of at least 10%, at least 15%, or at least 20%; the mole percent of elemental silicon may also be up to 35%, up to 40%, up to 45%, up to 50%, or up to 55%. For example, the mole percentage content of the simple substance 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%.
The second component of the nano silicon metal composite material can comprise a first component of transition metal, or a combination thereof, or a compound formed by the transition metal and the silicon, a second component of aluminum, tin, antimony, or a combination thereof, or a compound formed by the silicon, a third component of alkaline earth elements or a combination thereof, and a fourth component of carbon, oxygen, or a compound formed by the transition metal, the tin, the antimony, or the combination thereof and the silicon, or the compound formed by the transition metal and the silicon. A molar percentage of the second component of at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%; the mole percentage of the second component may 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 a part of the capacity, while other metals are not electrochemically active, and therefore, the molar percentage of the second component is more preferably 10 to 70%. For example, the second component may be present in an amount of 10 to 20%, 10 to 30%, 10 to 40%, 10 to 50%, 10 to 60%, 10 to 70%, 20 to 30%, 20 to 40%, 20 to 50%, 20 to 60%, 20 to 70%, 30 to 40%, 30 to 50%, 30 to 60%, 30 to 70%, 40 to 50%, 40 to 60% or 40 to 70% by mole.
Silicon-oxygen compound SiO in nano silicon metal composite materialxElemental silicon in the silicon dioxide which is not completely reduced in the raw material or the nano-silicon metal composite material which is the electrolysis product is oxidized again in the post-treatment process, so that the silicon-oxygen compound is attached to the surface of the elemental silicon. The content of the silicon oxide compound in the electrolytic product nano silicon metal composite material can be adjusted by controlling the electrolytic capacity, namely the electrolytic time. If the electrolysis time is controlled to be enough to completely electrolyze the raw material silicon dioxide, the nano silicon metal composite material does not contain silicon oxygen compound. The silicon oxide in the nano silicon metal composite material can embed lithium, and the lithium silicate attached to the surface of the nano silicon formed after lithium embedding has good conductivity and can effectively limit the volume change in the process of lithium embedding and lithium removing of silicon. Therefore, the silicon-oxygen compound in the nano silicon-metal composite material is beneficial to improving the cycle stability of the silicon-metal composite material, but lithium cannot be completely extracted by lithium silicate formed after the silicon-oxygen compound embeds lithium, so that the first coulombic efficiency of the nano silicon-metal composite material is lower. Therefore, the mol percentage of the silicon oxide compound in the nano silicon metal composite material is 0.1-5 mol%.
The nano silicon metal composite material has the following structural characteristics: the metal is one or more of spherical, spheroidal, flaky and linear; the simple substance silicon is in one or more of a linear shape, a granular shape, a tubular shape and a sheet shape. Wherein the simple substance silicon is at least one of nano silicon wire, nano silicon particle, nano silicon tube and nano silicon chip. The particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm. The simple substance carbon is one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape. The structure of the nano-silicon metal composite is related to the structure of each component part, and includes but may not be completely consistent with the structure of each component part.
The metal in the nano silicon metal composite material is derived from metal and metal oxide in raw materials and can be in a crystalline and/or amorphous state; the simple substance carbon in the nano silicon metal composite material is derived from a carbon material in the raw material, and can be a graphite negative electrode material commonly used in the field of lithium ion batteries, such as natural graphite, artificial graphite, mesocarbon microbeads and the like; the carbon material may be conductive carbon material for lithium ion battery, such as acetylene black, carbon fiber or carbon tube, etc., or 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.
The metal in the nano silicon metal composite material and silicon can generate metal silicide, and the metal silicide is mainly generated by slowly soaking the nano silicon and the metal in metal reduction silicon dioxide or molten salt for a long time in the electrode sintering process. The metal silicide can effectively improve the binding force between the simple substance silicon and the metal, improve the conductivity and inhibit the overlarge volume change of the silicon material in the lithium desorption process. Therefore, the uniformity of silicon dioxide and metal materials in the raw materials is ensured, and the generated silicon, metal and metal silicide can be uniformly combined together.
The preparation method of the nano silicon metal composite material provided by the invention comprises the following steps:
1. compounding a porous block consisting of metal, metal oxide and silicon dioxide with a conductive cathode current collector to serve as a cathode, taking graphite or an inert anode as an anode, placing the anode at a certain temperature, and adding CaCl2Or with CaCl2Applying voltage between cathode and anode in mixed salt melt electrolyte to electrolyze electric quantityAs the control means for finishing the electrolysis process, the silicon dioxide in the porous block is electrolyzed and reduced into nano silicon, and the nano silicon metal composite material is prepared at the cathode. The electrolysis time is the electric quantity needed by the theory and above when the electrolysis electric quantity reaches. The theoretically required electric quantity is the electric quantity calculated according to the electrons consumed by SiO2 to become simple substance Si, and the electric quantity changes along with the change of the content of SiO 2.
The structure (such as microscopic uniformity, porosity and pore diameter), composition and size of the porous block body composed of metal, metal oxide and silicon dioxide are key factors influencing the composition proportion, morphology and distribution uniformity of elemental silicon, metal silicide and silicon-oxygen compound of the electrolytic product nano-silicon metal composite material and the specific capacity of the lithium ion battery cathode material. The microscopic uniformity of the metal, the metal oxide and the silicon dioxide in the porous block body consisting of the metal, the metal oxide and the silicon dioxide can directly influence the distribution uniformity of the simple substance silicon, the metal and the metal silicide of the electrolytic product nano silicon metal composite material, so that the porous block body which is uniformly mixed must be manufactured. When the porosity of the porous electric block body consisting of the metal and the silicon dioxide is large, for example, when the porosity of the porous block body is more than 60%, the volume of the silicon generated by electrolytic reduction of the silicon dioxide in the electrolytic process is reduced by 50% due to the release of oxygen, and the porosity of the porous block body consisting of the metal and the silicon is increased after reduction, so that the strength of the porous block body is not enough and the porous block body cannot be completely taken out of the molten salt. When the porosity of the porous block composed of metal and silica is small, for example, when the porosity of the porous block is less than 5 vol%, the pores in the porous block for molten electrolyte calcium chloride to pass through are small, the electrolytic reduction reaction speed is reduced, and the electrolysis time is too long, so that the content of metal silicide in the product is too large.
The specific implementation process of compounding the porous block body consisting of metal, metal oxide and silicon dioxide and the conductive cathode current collector to be used as the cathode comprises the steps of firstly preparing silicon dioxide powder into silicon dioxide colloid, adding the metal and the metal oxide into the silicon dioxide colloid, carrying out high-speed mechanical fusion to ensure that the silicon dioxide is uniformly coated on the metal oxide and the metal to form a mixture, then preparing the mixture into a block green body, forming the porous block body by the block green body at a certain mechanical pressure or a certain temperature, wherein the porous block body is prepared at the mechanical pressure of 10-100 MPa and the temperature of 800-1400 ℃, and the porosity of the obtained porous block body is 10-30%.
2. According to the preparation method of step 1, the metal powder in the raw material is spherical, spheroidal, flaky or linear.
3. According to the preparation method in step 1, the metal oxide in the raw material is in a powder form.
4. According to the preparation method described in step 1, the silica powder refers to silica particles with an average particle size of 10nm to 1 μm.
5. The preparation method according to the step 1, wherein the CaCl is adopted2The main mixed salt melt electrolyte is CaCl2+MY1Wherein M is Ba, Li, Al, Cs, Na, K, Mg, Rb, Be or Sr, Y1Is Cl or F.
6. According to the preparation method of the step 1, the electrolysis voltage is lower than the theoretical decomposition voltage of the electrolyte, and the electrolysis electric quantity is the electric quantity required by the theory and above for the electrolysis electric quantity.
7. According to the preparation method described in step 1, electrolysis is carried out at a temperature of 500-1000 ℃.
8. According to the preparation method of the step 1, after the electrolysis process is finished, the product can be taken out of the molten salt along with the working electrode, and if necessary, a porous block electrode consisting of metal or metal oxide and silicon dioxide can be put in the molten salt to start a new round of electrolysis, so that the continuous production of the nano silicon metal composite material is realized.
9. According to the preparation method of the step 1, after an electrolysis product is taken out, the electrolysis product is cooled to room temperature under an inert atmosphere, and then the electrolysis product is fully washed in water and an organic solvent, and molten salt electrolyte included in the electrolysis product is removed.
10. According to the preparation method described in the step 1, the washed electrolysis product is dried in vacuum for more than 12 hours.
11. According to the preparation method of the step 1, the dried electrolytic product is ground, crushed and sieved to obtain the nano silicon metal composite material.
The following examples illustrate the invention, the "nano SiO" in the raw materials described in the examples2The powder "means a powder having a particle size of 100nm or less.
Example 1
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 30 mol% of spheroidal nickel powder which is sold in the market and has the diameter of 2-10 mu m, 10 mol% of nickel protoxide which is sold in the market and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, wherein the porous block is prepared into a porous block body with the mechanical pressure of 14MPa and the temperature of 900 ℃, the porosity of the obtained porous block body is 30 volume percent, and the density is 1.3 g/cm3The conductivity is 0.8 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.2V. After 8 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel-loaded nano silicon particle composite material shown in figure 1, nickel silicide exists between nickel and nano silicon particles discontinuously, and silicon oxide SiO existsxIs present on the surface of the nano silicon particles. The prepared nickel-loaded nano silicon particle composite material contains 38 mol percent of simple substance nickel, 55mol percent of simple substance silicon and nickel silicide (NiSi)2) 5% by mol of a silicon oxide SiO22%, 55 Si/45 (Ni)38(NiSi2)5(giO2)2). The simple substance silicon in the composite material is in a crystalline state, the simple substance silicon is in a granular state and a linear state, the grain diameter of the granular simple substance silicon is less than 100nm, and the diameter of the linear simple substance silicon is less than 100 nm.
The obtained composite material is used for preparing the lithium ion battery electrode by taking the prepared electrolytic product nano silicon-nickel composite material as an active substance, Super-P carbon black as a conductive agent and PVDF as a binder, uniformly mixing the materials according to the mass ratio of 7: 2: 1, then using N-methyl pyrrolidone as a solvent for size mixing, coating the size on copper foil with the thickness of 8 mu m to prepare a pole piece with the thickness of 1.0cm × 1.5cm, drying the pole piece at 70 ℃, rolling the pole piece to the required thickness, drying the pole piece for 12 hours at 120 ℃ in vacuum, taking a metal lithium piece as a counter electrode, using a Celgard2300 film as a diaphragm and 1 mol/LLiPF6The electrolyte solution is prepared into an experimental battery (the diameter phi is 30mm, and the length L is 100mm) by self design, wherein the volume ratio of the electrolyte solution to the DEC + DMC is 1: 1: 1. The charging and discharging performance of the experimental battery is tested by a blue battery testing system CT2001A tester. The charge-discharge voltage range is 0.005-2.0V, the charge-discharge current density is 80 mA/g, and the capacity retention rate C of the battery for 100 cycles is tested100／C1。
Example 2
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 14MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 23 volume percent, and the density of the porous block is 1.4 g/cm3The conductivity is 1.2 omega 2 cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and C is usedaCl2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.4V. After 7 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 53 Si/47 (Ni)35(NiSi2)8(SiO2)4). As shown in FIG. 3, the crystalline components in the obtained composite material are mainly composed of elemental Si, Ni and NiSi compounds.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 3
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 20 mol% of spheroidal nickel powder which is commercially available and has the diameter of 2-10 mu m, 30 mol% of nickel protoxide which is commercially available and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 14MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 15 volume percent, and the density of the porous block is 1.25 g/cm3The conductivity is 1.5 omega 2 cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 6 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded silicon nanowire composite material 45 Si/55 (Ni)48(NiSi)5(SiO2)2)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 4
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 40 mol% of spheroidal nickel powder which is commercially available and has the diameter of 2-10 mu m, 10 mol% of nickel protoxide which is commercially available and has the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body at a certain mechanical pressure or a certain temperature, wherein the porous block is prepared into a porous block body with the mechanical pressure of 14MPa and the temperature of 900 ℃, the porosity of the obtained porous block body is 29 volume percent, and the density is 1.5 g/cm3The conductivity is 0.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 800 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 18 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the composite material 40 Si/60 (Ni) of the nano silicon wire growing on the nickel powder42(NiSi)15(SiO2)3)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 5
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 20 mol% of nickel fiber with the diameter of 1-5 μm sold on the market, 10 mol% of spherical iron powder and 10 mol% of nickel protoxide with the purity of 98 wt% sold on the market into the colloid, and increasing the content of nickel protoxideQuick mechanical fusion, so that the 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 body under certain mechanical pressure or certain temperature, the mechanical pressure of the porous block body is 15MPa, the temperature of the porous block body is 900 ℃, the porosity of the obtained porous block body is 25 volume percent, and the density is 1.1 g/cm3The conductivity is 0.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the silicon metal nanowire composite material 54 Si/46 (Ni)27Fe8(NiSi2)5(FeSi2)2(Fe2O3)2(SiO2)2)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 6
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 12 mol% of commercially available nickel fiber with the diameter of 1-5 mu m, 20 mol% of spherical iron powder and 8 mol% of commercially available nickel protoxide with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 20MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 15 volume percent, and the density of the porous block is 1.2 g/cm3The conductivity is 1.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, and the graphite rod is used as an anodeVery much of CaCl2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.8V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the silicon metal nanowire composite material 52 Si/48 (Ni)18Fe17(NiSi2)3(FeSi2)4(Fe2O3)5(SiO2)1)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 7
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, adding 6 mol% of commercially available nickel fiber with the diameter of 1-5 mu m, 14 mol% of commercially available nickel protoxide with the purity of 98 wt% and 30 mol% of commercially available carbon fiber with the diameter of 20-200 nm and the length of 5-10 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 20MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 27 volume percent and the density of the obtained porous block body is 0.8 g/cm3The conductivity is 0.2 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaC1 is used2The electrolyte is prepared by performing constant voltage electrolysis at 800 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 22 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product of the nano silicon metal carbon composite material 46 Si/26 (Ni)18(NiSi)48iC3(SiO2)1)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 8
55 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 5 mol% of spheroidal titanium powder sold in the market with the diameter of 2-5 mu m, 10 mol% of titanium dioxide sold in the market with the purity of 98 wt% and 30 mol% of coke with the particle size of 11-15 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, then preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 10MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 30 volume percent and the density is 1.3 g/cm3The conductivity is 0.5 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After the electrolysis for 11 hours, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product 53 Si-metal-carbon nano-composite material53／19(Ti12(TiSi2)3SiC3(SiO2)1) and/28C. The simple substance silicon in the composite material is in a crystalline state, the simple substance silicon is in a granular state and a linear state, the grain diameter of the granular simple substance silicon is less than 100nm, and the diameter of the linear simple substance silicon is less than 100 nm. The carbon in the composite material is spherical or quasi-spherical.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 9
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 4 mol% of spheroidal nickel powder with the diameter of 2-10 mu m sold on the market, 10 mol% of nickel fiber with the diameter of 2-10 m sold on the market, 6 mol% of nickel protoxide with the purity of 98 wt% and 30 mol% of carbon fiber with the diameter of 20-200 nm and the length of 5-10 mu m into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 30MPa, the porous block body preparing temperature of 900 ℃, and obtaining the porous block body with the porosity of 14 vol% and the density of 1.8 g/cm3The conductivity is 0.3 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product of the nano silicon metal carbon composite material 47Si/25 (Ni)17(NiSi)48iC2(SiO2)2)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 10
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, preparing 2 mol% of a spherical-like aluminum powder having a diameter of 2 to 10 μm on the market, 10 mol% of a tin powder having a diameter of 2 to 10 μm on the market, 4 mol% of an alumina having a purity of 98 wt% and 30 mol% of an aluminum powder having a diameter of 20 to 200nm,adding carbon fibers with the length of 5-10 mu m into the colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block body with the mechanical pressure of 20MPa and the porous block body preparation temperature of 900 ℃, and obtaining the porous block body with the porosity of 20 volume percent and the density of 1.1 g/cm3The conductivity is 0.3 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.6V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product 48 Si/24 (Al) nano silicon metal carbon composite material9Sn10SiC3(SiO2)2)／28C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 11
50 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 10 mol% of commercially available tin powder with the diameter of 2-10 mu m, 5 mol% of titanium dioxide with the purity of 98 wt% and 35 mol% of graphite flakes with the particle size of 3-6 mu m into colloid, performing high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 15MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block is 18 volume percent and the density of the obtained porous block is 1.4 g/cm3The conductivity is 0.2 omega cm, and the porous block body is compounded with a conductive cathode current collectorAs cathode, graphite rod as anode, CaCl2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.7V. After 20 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the product of the nano silicon metal carbon composite material 48 Si/81 (Ti)4Sn10(TiSi2)1SiC2(SiO2)2)／33C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 12
20 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 10 mol% of spherical nickel powder with the diameter of 2-10 mu m sold on the market, 5 mol% of titanium dioxide with the purity of 98 wt% and 65 mol% of graphite flake with the particle size of 3-6 mu m into colloid, adding high-speed mechanical fusion to ensure that the silicon dioxide is uniformly coated on metal, metal oxide and carbon to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 25MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block is 10 volume percent and the density of the obtained porous block is 1.9 g/cm3The conductivity is 0.1 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2Using a voltage stabilizer to control the voltage to carry out constant voltage electrolysis at 900 ℃ in an argon environment, using a voltage stabilizer to control the voltage to carry out electrolysis for 20 hours at the cell voltage of 2.7V3, washing the electrolysis product with water and absolute ethyl alcohol in sequence, drying in vacuum, and sieving to obtain the silicon metal carbon nanowire composite material 17 Si/20 (Ti is Ti4Ni8(TiSi)1(NiSi)28iC3(SiO2)2)／63C。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 13
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 30MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 10 volume percent, and the density is 1.6 g/cm3The conductivity is 2.1 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 10 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 50 Si/50 (Ni)35(NiSi)9(SiO2)6)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 14
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: 1, 20 mol% of the product is sold on the marketAdding spheroidal nickel powder with the diameter of 2-10 mu m and 20 mol% of commercially available nickel protoxide with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact at a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 25MPa and the porous block preparing temperature of 900 ℃, wherein the porosity of the obtained porous block is 15 volume percent and the density is 1.55 g/cm3The conductivity is 1.7 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 9.2 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 51 Si/49 (Ni)35(NiSi)9(SiO2)5)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 15
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m and 20 mol% of nickel protoxide sold in the market with the purity of 98 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, then preparing the mixture into a block green compact, forming a porous block by the block green compact under a certain mechanical pressure or a certain temperature, wherein the mechanical pressure of the porous block is 20MPa, the temperature of the porous block is 900 ℃, the porosity of the obtained porous block is 20 volume percent, and the density is 1.5 g/cm3The conductivity is 1.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, and stone is usedInk stick as anode, CaCl2The electrolyte is prepared by performing constant voltage electrolysis at 850 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 8 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 52 Si/48 (Ni)35(NiSi)9(SiO2)4)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 16
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold on the market with the diameter of 2-10 mu m, 10 mol% of nickel protoxide sold on the market with the purity of 98 wt% and 10 mol% of spherical graphite negative electrode material BTR-918 sold on the market into colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metal nickel to form a mixture, preparing the mixture into a block green body, forming a porous block body by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block body into a porous block body with the mechanical pressure of 15MPa and the temperature of 900 ℃, wherein the porosity of the obtained porous block body is 22 volume percent and the density is 1.43 g/cm3The conductivity is 1.4 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 950 deg.C under argon atmosphere and with a voltage regulator at 2.5V. After 7.5 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 53 Si/37 (Ni)25(NiSi)9(SiO2)3) And 10C. Example 16 a scanning electron microscope image of a silicon-based metal carbon nanowire composite prepared at 950 ℃ is shown in fig. 2.
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
Example 17
60 mol% of nano SiO with the purity of 99.95 wt%2Adding water into the powder, stirring to form silicon dioxide colloid, wherein the mass ratio of the water to the SiO2 is 2: adding 20 mol% of spheroidal nickel powder sold in the market with the diameter of 2-10 mu m, 19 mol% of nickel protoxide sold in the market with the purity of 98 wt% and 1 mol% of calcium oxide sold in the market with the purity of 99 wt% into a colloid, carrying out high-speed mechanical fusion to ensure that silicon dioxide is uniformly coated on metallic nickel to form a mixture, preparing the mixture into a block green body, forming a porous block by the block green body under a certain mechanical pressure or a certain temperature, preparing the porous block into a porous block with the mechanical pressure of 20MPa and the temperature of 1000 ℃, wherein the porosity of the obtained porous block is 13 volume percent and the density is 1.56 g/cm3The conductivity is 2.9 omega cm, the porous block body and the conductive cathode current collector are compounded to be used as a cathode, the graphite rod is used as an anode, and CaCl is used2The electrolyte is prepared by performing constant voltage electrolysis at 900 deg.C under argon atmosphere, and the cell voltage is 2.5V. After 11 hours of electrolysis, the electrolysis product is washed by water and absolute ethyl alcohol in sequence, dried in vacuum and sieved to obtain the nickel powder loaded nano silicon particle composite material 50 Si/50 (Ni)35(NiSi)8(CaSi)(SiO2)6)。
The obtained composite material was subjected to electrochemical performance test by preparing an electrode in the same manner as in example 1, and the electrochemical performance of the test is shown in table 1.
The results of the electrochemical performance tests of the examples were compared and are shown in table 1. Compared with the test result, under the same controlled electrolysis condition, the sample with high content of SiO2 in the raw material has higher lithium intercalation capacity for the first time, but the first coulombic efficiency is lower.
TABLE 1 electrochemical Properties of the Nanosilicon carbon composite
Claims (22)
1. The nano silicon metal composite material for the lithium ion battery is characterized by comprising the following components in parts by weight:
(a) the first component is simple substance silicon, and the content of the simple substance silicon is 5-75 mol% relative to the nano silicon metal composite material;
(b) the second component part comprises a metal element, a compound formed by the metal element and silicon and a silicon-oxygen compound, and the content of the second component part is 25-95 mol% relative to the nano silicon composite material;
(c) the third component is simple substance carbon, and the content of the simple substance carbon is 0-70 mol% relative to the nano silicon metal composite material.
2. The nano-silicon metal composite material for the lithium ion battery according to claim 1, wherein the second component of the nano-silicon metal composite material for the lithium ion battery further comprises one or more of a compound formed by a metal element and a metal element, a compound formed by a metal element and carbon, a compound formed by a metal element and oxygen, and a silicon carbon compound.
3. The nano-silicon metal composite material for the lithium ion battery according to claim 1, wherein the metal element in the second component part is one or more of transition metal elements, aluminum, tin, antimony and alkaline earth elements.
4. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the molar percentage of the simple substance silicon is 10-55 mol%.
5. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance silicon is one or more of granular, linear, tubular and flaky.
6. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance silicon is in a crystalline state or/and an amorphous state.
7. The nano-silicon metal composite material for a lithium ion battery according to claim 5, characterized in that: the particle size of the granular simple substance silicon is less than 100nm, the diameter of the linear simple substance silicon is less than 100nm, the diameter of the tubular simple substance silicon is less than 100nm, and the thickness of the flaky simple substance silicon is less than 100 nm.
8. The nano-silicon metal composite material for a lithium ion battery according to claim 1, characterized in that: the simple substance carbon is in one or more of spherical shape, similar spherical shape, sheet shape, linear shape and tubular shape.
9. The nano-silicon metal composite material for a lithium ion battery according to claim 2, characterized in that: the silicon carbon compound SiC of the second component of the nano silicon metal composite material for the lithium ion battery is one or more of granular, linear and flaky.
10. The nano-silicon metal composite material for a lithium ion battery according to claim 9, characterized in that: the grain diameter of the granular SiC is less than 100nm, the diameter of the linear SiC is less than 100nm, and the thickness of the sheet SiC is less than 100 nm.
11. The nano-silicon metal composite material for a lithium ion battery according to claim 3, characterized in that: wherein the transition metal element in the second component is nickel, titanium, iron, copper, cobalt, manganese, zinc, silver, gold, or a combination thereof.
12. The nano-silicon metal composite material for a lithium ion battery according to claim 3, characterized in that: wherein the alkaline earth element in the second component is magnesium, calcium, strontium, barium, or a combination thereof.
13. The nano-silicon metal composite for a lithium ion battery according to any one of claims 1 to 12, wherein: the silicon metal composite material has a general formula I:
xSi/y(NfHdKe)/zC (I)
wherein,
n is a metal element, and a compound thereof with silicon;
h is one or more of compounds formed by carbon element and one selected from Si and metal elements;
k is one of compounds of oxygen and Si or one of compounds of oxygen and Si and one or more of compounds formed by oxygen and metal elements;
wherein the metal element is one or more of transition metal element, aluminum, tin, antimony and alkaline earth element;
x is the mole percentage of the first component, namely silicon, in the nano silicon metal composite material, and the x is 5-75 mol%;
y is the mole percentage of the second component in the nano silicon metal composite material, and y is 25-95 mol%;
z is the mole percentage of carbon in the nano silicon metal composite material, and z is 0-70 mol%;
wherein x + y + z is 100 mol%;
f, d, e are the mole percentages of N, H and K in the second component part, respectively; f is 10-90 mol%; d is 0-10 mol%; e is 10 to 90 mol%, and f + d + e is 100 mol%.
14. A method for preparing the nano-silicon metal composite material for the lithium ion battery of any one of claims 1 to 13, which is characterized in that: using a porous block consisting of silicon dioxide powder containing at least metal M or metal oxide MO as a cathode, graphite or an inert anode as an anode, CaCl2Or with CaCl2And (2) taking the mixed salt melt as a main electrolyte to form an electrolytic bath, applying direct current voltage between a cathode and an anode, and controlling the electrolytic current density and electrolytic electric quantity to ensure that the silicon dioxide or the silicon dioxide and the metal oxide in the porous block are subjected to in-situ electrolytic reduction at the cathode to prepare the nano silicon metal composite material for the lithium ion battery, wherein M is one or more elements selected from transition metal elements, aluminum, tin, antimony and alkaline earth elements.
15. The method of claim 14, wherein: the porous block may also contain carbon.
16. The method of claim 15, wherein: the porous block body composed of the silicon dioxide powder at least containing the metal M or the metal oxide MO is formed by preparing the silicon dioxide powder into silicon dioxide colloid, uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO to form a mixture, and preparing the mixture into the porous block body.
17. The method of claim 16, wherein: and uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO and the carbon.
18. The method of claim 14, wherein: the porous block body composed of the silicon dioxide powder at least containing the metal M or the metal oxide MO is formed by preparing the silicon dioxide powder into silicon dioxide colloid, uniformly coating the silicon dioxide colloid on one or two of the metal M and the metal oxide MO to form a mixture, and preparing the mixture into the porous block body.
19. The method of claim 14, wherein: the particle size of the silicon dioxide powder is 10nm to 1 mu m.
20. The method of claim 14, wherein: the porosity of the porous block is 1-40 vol%.
21. The method of claim 20, wherein: the porosity of the porous block is 10-30 vol%.
22. A lithium ion battery, the battery includes positive pole, negative pole and nonaqueous electrolyte, characterized by that: the negative electrode comprises the nano-silicon metal composite material as claimed in any one of claims 1 to 13.
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