JPWO2015182124A1 - シリコン材料及び二次電池の負極 - Google Patents
シリコン材料及び二次電池の負極 Download PDFInfo
- Publication number
- JPWO2015182124A1 JPWO2015182124A1 JP2016523148A JP2016523148A JPWO2015182124A1 JP WO2015182124 A1 JPWO2015182124 A1 JP WO2015182124A1 JP 2016523148 A JP2016523148 A JP 2016523148A JP 2016523148 A JP2016523148 A JP 2016523148A JP WO2015182124 A1 JPWO2015182124 A1 JP WO2015182124A1
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- negative electrode
- secondary battery
- active material
- electrode active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 76
- 239000007773 negative electrode material Substances 0.000 claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 25
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 description 41
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 35
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 29
- 239000002253 acid Substances 0.000 description 22
- 239000011230 binding agent Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 16
- 239000011737 fluorine Substances 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000000862 absorption spectrum Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229910052814 silicon oxide Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 230000031700 light absorption Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910004706 CaSi2 Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- -1 hexafluoroarsenic acid Chemical compound 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910021348 calcium disilicide Inorganic materials 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000011246 composite particle Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 229920000548 poly(silane) polymer Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000011856 silicon-based particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
-
- 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
- H01M10/02—Details
-
- 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
- H01M4/134—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Power Engineering (AREA)
- Composite Materials (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
Description
本発明のシリコン材料は、バンドギャップが1.1eVを超えかつ2.1eV以下の範囲にある。バンドギャップが1.2eV〜1.6eVの範囲にあることが特に望ましい。前述した非特許文献2には、バンドギャップを算出したことが記載され、層状シリコン化合物のアニール条件によってシリコン材料のバンドギャップが変化することが記載されている。しかしバンドギャップと電池特性との関係に関しては、記載も示唆もない。
本発明のシリコン材料は、酸とCaSi2とを反応させて得られた層状シリコン化合物を非酸化性雰囲気にて350℃〜950℃程度で熱処理することで製造することができる。用いる酸としては、非特許文献2に記載されたように塩酸(HCl)を用いてもよいし、少なくともアニオンにフッ素を含む酸を用いることも好ましい。少なくともアニオンにフッ素を含む酸を用いることで、層状シリコン化合物及びシリコン材料に含まれる酸素(O)量を低減することができる。またフッ素(F)を含むことで、塩素(Cl)量をゼロ若しくは低減できる。したがって本発明のフッ素を含むシリコン材料をリチウムイオン二次電池の負極活物質などに用いた場合には、初期容量が好適に向上する。
層状シリコン化合物製造工程において、少なくともアニオンにフッ素を含む酸としてフッ化水素酸(HF)を用いる場合は、塩酸(HCl)を混合して用いることが好ましい。フッ化水素酸(HF)のみを用いた場合でも層状シリコン化合物が得られるものの、得られる層状シリコン化合物は活性が高く微量の空気によって酸化され、酸素量が増大するため好ましくない。また塩酸(HCl)のみを用いた場合は、非特許文献1,2と同様であり、酸素量が多い層状シリコン化合物しか得られない。
本発明のシリコン材料は、リチウムイオン二次電池などの二次電池における負極活物質として用いることができる。本発明のシリコン材料を用いて、例えば非水系二次電池の負極を作製するには、本発明のシリコン材料を含む負極活物質粉末と、炭素粉末などの導電助剤と、バインダーと、適量の有機溶剤を加えて混合しスラリーにしたものを、ロールコート法、ディップコート法、ドクターブレード法、スプレーコート法、カーテンコート法などの方法で集電体上に塗布し、バインダーを乾燥あるいは硬化させることによって作製することができる。
い。セパレータは、正極と負極とを分離し電解液を保持するものであり、ポリエチレン、ポリプロピレン等の薄い微多孔膜を用いることができる。
濃度36質量%のHCl水溶液65mlを氷浴中で0℃とし、アルゴンガス気流中にてそこへ3.3gの二ケイ化カルシウム(CaSi2)を加えて撹拌した。発泡が完了したのを確認した後に室温まで昇温し、室温でさらに2時間撹拌した後、蒸留水20mlを加えてさらに10分間撹拌した。このとき黄色粉末が浮遊した。得られた混合溶液を濾過し、残渣を10mlの蒸留水で洗浄した後、10mlのエタノールで洗浄し、真空下で12時間乾燥して3.5gの層状シリコン化合物を得た。
実施例1と同様に製造された層状シリコン化合物を用い、熱処理温度を700℃としたこと以外は実施例1と同様にしてシリコン材料を得た。
実施例1と同様に製造された層状シリコン化合物を用い、熱処理温度を800℃としたこと以外は実施例1と同様にしてシリコン材料を得た。
実施例1と同様に製造された層状シリコン化合物を用い、熱処理温度を900℃としたこと以外は実施例1と同様にしてシリコン材料を得た。
実施例1と同様に製造された層状シリコン化合物を用い、熱処理温度を300℃としたこと以外は実施例1と同様にしてシリコン材料を得た。
濃度46質量%のHF水溶液2mlと、濃度36質量%のHCl水溶液63mlとの混合溶液を氷浴中で0℃とし、アルゴンガス気流中にてそこへ3.3gの二ケイ化カルシウム(CaSi2)を加えて撹拌した。発泡が完了したのを確認した後に室温まで昇温し、室温でさらに2時間撹拌した後、蒸留水20mlを加えてさらに10分間撹拌した。このとき黄色粉末が浮遊した。
実施例6と同様に製造された層状シリコン化合物を用い、熱処理温度を700℃としたこと以外は実施例6と同様にしてシリコン材料を得た。
実施例6と同様に製造された層状シリコン化合物を用い、熱処理温度を900℃としたこと以外は実施例6と同様にしてシリコン材料を得た。
実施例6と同様に製造された層状シリコン化合物を用い、熱処理温度を300℃としたこと以外は実施例6と同様にしてシリコン材料を得た。
市販の結晶シリコン(レアメタリック社製)を比較例1とした。この結晶シリコンについて、光吸収スペクトルの吸収端波長からバンドギャップを算出したところ、表1にも示すように1.1eVであった。
市販のSiOx(x=0.5〜1.6)(「酸化ケイ素」大阪チタニウム社製)を比較例2とした。このSiOxについて、光吸収スペクトルの吸収端波長からバンドギャップを算出したところ、表1にも示すように1.8eVであった。Si/O原子比は1/1.1である。
各実施例及び各比較例のシリコン材料それぞれ45質量部と、天然黒鉛粉末40質量部と、アセチレンブラック5質量部と、バインダー溶液33質量部とを混合してそれぞれのスラリーを調製した。バインダー溶液には、ポリアミドイミド(PAI)樹脂がN-メチル-2-ピロリドン(NMP)に30質量%溶解した溶液を用いている。これらのスラリーを、厚さ約20μmの電解銅箔(集電体)の表面にドクターブレードを用いてそれぞれ塗布し、乾燥して銅箔上に負極活物質層を形成した。その後、ロールプレス機により、集電体と負極活物質層を強固に密着接合させた。これを100℃で2時間真空乾燥し、負極活物質層の目付け量が2.0mg/cm2、電極密度が1.0g/cm3の負極をそれぞれ形成した。
各実施例及び各比較例のリチウム二次電池について、電流:0.1C、電圧:0.01-0.8Vの条件で、それぞれ50サイクルの充放電試験を行った。初期の充電容量と放電容量を測定し、初期効率(100×放電容量/充電容量)を算出した結果を表1に示す。また初期の放電容量に対する50サイクル後の放電容量の割合である容量維持率を算出し、寿命として表1に示す。さらに、バンドギャップと容量維持率との関係を図2に、バンドギャップと初期効率との関係を図3に示す。
Claims (5)
- Si/O原子比が1/0.5を超えかつ1/0.1以下の範囲にあり、バンドギャップが1.1eVを超えかつ2.1eV以下の範囲にあることを特徴とするシリコン材料。
- ナノサイズのシリコン結晶子を含む請求項1に記載のシリコン材料。
- 請求項1又は請求項2に記載のシリコン材料からなることを特徴とする負極活物質。
- 請求項3に記載の負極活物質を含むことを特徴とする負極。
- 請求項4に記載の負極を有することを特徴とする二次電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014110835 | 2014-05-29 | ||
JP2014110835 | 2014-05-29 | ||
PCT/JP2015/002653 WO2015182124A1 (ja) | 2014-05-29 | 2015-05-26 | シリコン材料及び二次電池の負極 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2015182124A1 true JPWO2015182124A1 (ja) | 2017-04-20 |
JP6176511B2 JP6176511B2 (ja) | 2017-08-09 |
Family
ID=54698471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016523148A Active JP6176511B2 (ja) | 2014-05-29 | 2015-05-26 | シリコン材料及び二次電池の負極 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10217990B2 (ja) |
EP (1) | EP3150554B1 (ja) |
JP (1) | JP6176511B2 (ja) |
KR (1) | KR101841871B1 (ja) |
CN (1) | CN106414324B (ja) |
CA (1) | CA2950251C (ja) |
RU (1) | RU2650976C1 (ja) |
WO (1) | WO2015182124A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111742437A (zh) * | 2018-02-27 | 2020-10-02 | 松下知识产权经营株式会社 | 非水电解质二次电池 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006009073A1 (ja) * | 2004-07-16 | 2006-01-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | シリコンナノシート、ナノシート溶液及びその製造方法、ナノシート含有複合体、並びに、ナノシート凝集体 |
JP2012244014A (ja) * | 2011-05-20 | 2012-12-10 | Osaka Gas Chem Kk | 光電変換材料および太陽電池 |
WO2013066669A2 (en) * | 2011-11-01 | 2013-05-10 | Nanogram Corporation | Structures incorporating silicon nanoparticle inks, densified silicon materials from nanoparticle silicon deposits and corresponding methods |
JP2013191329A (ja) * | 2012-03-13 | 2013-09-26 | Toyota Industries Corp | 非水電解質二次電池および車両 |
WO2013163417A1 (en) * | 2012-04-26 | 2013-10-31 | King Abdullah University Of Science And Technology | Colloidal photoluminescent amorphous porous silicon, methods of making colloidal photoluminescent amorphous porous silicon, and methods of using colloidal photoluminescent amorphous porous silicon |
JP2014022319A (ja) * | 2012-07-23 | 2014-02-03 | Toyota Industries Corp | 二次電池用負極活物質、その製造方法、二次電池用負極、二次電池、及びSi−酸化物固体電解質複合体 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4392011A (en) | 1980-04-30 | 1983-07-05 | Rca Corporation | Solar cell structure incorporating a novel single crystal silicon material |
US5538675A (en) | 1994-04-14 | 1996-07-23 | The Dow Chemical Company | Method for producing silicon nitride/silicon carbide composite |
JPH1012889A (ja) | 1996-06-18 | 1998-01-16 | Semiconductor Energy Lab Co Ltd | 半導体薄膜および半導体装置 |
JP3865033B2 (ja) | 2000-02-04 | 2007-01-10 | 信越化学工業株式会社 | 酸化珪素粉末の連続製造方法及び連続製造装置 |
JP4938960B2 (ja) | 2003-11-07 | 2012-05-23 | 哲雄 碇 | 光電変換装置の製造方法及び光電変換装置 |
US8231810B2 (en) * | 2004-04-15 | 2012-07-31 | Fmc Corporation | Composite materials of nano-dispersed silicon and tin and methods of making the same |
KR100851969B1 (ko) * | 2007-01-05 | 2008-08-12 | 삼성에스디아이 주식회사 | 음극 활물질, 그 제조 방법 및 이를 채용한 음극과 리튬전지 |
JP4915262B2 (ja) * | 2007-03-23 | 2012-04-11 | 株式会社豊田中央研究所 | 非水系蓄電デバイス及びそれに用いられる電極 |
JP2009102219A (ja) | 2007-10-02 | 2009-05-14 | Hitachi Ltd | 光学ガラス |
US8053382B2 (en) | 2007-10-02 | 2011-11-08 | Hitachi, Ltd. | Optical glass |
US20090186267A1 (en) | 2008-01-23 | 2009-07-23 | Tiegs Terry N | Porous silicon particulates for lithium batteries |
JP5446699B2 (ja) * | 2008-10-28 | 2014-03-19 | 株式会社豊田中央研究所 | シリコンナノシート、その製法及びリチウムイオン二次電池 |
JP5417859B2 (ja) * | 2009-01-22 | 2014-02-19 | 日産自動車株式会社 | ポリマーブレンドフィルムを含む電極 |
JP5471284B2 (ja) | 2009-10-20 | 2014-04-16 | 株式会社豊田中央研究所 | リチウム二次電池用電極及びそれを備えたリチウム二次電池 |
JPWO2012057253A1 (ja) | 2010-10-27 | 2014-05-12 | 国立大学法人 東京大学 | 蛍光シリコンナノ粒子及びその製造方法 |
KR101453967B1 (ko) | 2012-02-20 | 2014-10-29 | 고려대학교 산학협력단 | 다중 밴드갭 적층형 태양전지 및 다중 밴드갭 적층형 태양전지 형성 방법 |
JP6065678B2 (ja) | 2013-03-18 | 2017-01-25 | 株式会社豊田自動織機 | 負極活物質とその製造方法及び蓄電装置 |
-
2015
- 2015-05-26 WO PCT/JP2015/002653 patent/WO2015182124A1/ja active Application Filing
- 2015-05-26 JP JP2016523148A patent/JP6176511B2/ja active Active
- 2015-05-26 CN CN201580027617.5A patent/CN106414324B/zh active Active
- 2015-05-26 EP EP15800022.4A patent/EP3150554B1/en active Active
- 2015-05-26 RU RU2016151186A patent/RU2650976C1/ru active
- 2015-05-26 US US15/314,246 patent/US10217990B2/en active Active
- 2015-05-26 CA CA2950251A patent/CA2950251C/en active Active
- 2015-05-26 KR KR1020167031287A patent/KR101841871B1/ko active IP Right Grant
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006009073A1 (ja) * | 2004-07-16 | 2006-01-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | シリコンナノシート、ナノシート溶液及びその製造方法、ナノシート含有複合体、並びに、ナノシート凝集体 |
JP2012244014A (ja) * | 2011-05-20 | 2012-12-10 | Osaka Gas Chem Kk | 光電変換材料および太陽電池 |
WO2013066669A2 (en) * | 2011-11-01 | 2013-05-10 | Nanogram Corporation | Structures incorporating silicon nanoparticle inks, densified silicon materials from nanoparticle silicon deposits and corresponding methods |
JP2013191329A (ja) * | 2012-03-13 | 2013-09-26 | Toyota Industries Corp | 非水電解質二次電池および車両 |
WO2013163417A1 (en) * | 2012-04-26 | 2013-10-31 | King Abdullah University Of Science And Technology | Colloidal photoluminescent amorphous porous silicon, methods of making colloidal photoluminescent amorphous porous silicon, and methods of using colloidal photoluminescent amorphous porous silicon |
JP2014022319A (ja) * | 2012-07-23 | 2014-02-03 | Toyota Industries Corp | 二次電池用負極活物質、その製造方法、二次電池用負極、二次電池、及びSi−酸化物固体電解質複合体 |
Non-Patent Citations (1)
Title |
---|
SHUNSUKE KASASHIMA ET AL.: "Low concentrator hetero-junction microcrystalline silicon solar cells", JOURNAL OF NON-CRYSTALLINE SOLIDS, vol. Volume 358, Issue 17, JPN6015031759, 1 September 2012 (2012-09-01), pages 2260 - 2263, ISSN: 0003580101 * |
Also Published As
Publication number | Publication date |
---|---|
WO2015182124A1 (ja) | 2015-12-03 |
CA2950251C (en) | 2019-06-25 |
RU2650976C1 (ru) | 2018-04-18 |
EP3150554A1 (en) | 2017-04-05 |
EP3150554B1 (en) | 2018-07-11 |
US10217990B2 (en) | 2019-02-26 |
KR101841871B1 (ko) | 2018-03-23 |
CN106414324A (zh) | 2017-02-15 |
JP6176511B2 (ja) | 2017-08-09 |
US20170194623A1 (en) | 2017-07-06 |
CA2950251A1 (en) | 2015-12-03 |
EP3150554A4 (en) | 2017-05-10 |
CN106414324B (zh) | 2019-08-16 |
KR20160143791A (ko) | 2016-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014080608A1 (ja) | ナノシリコン材料及び負極活物質とその製造方法及び蓄電装置 | |
JP6288257B2 (ja) | ナノシリコン材料とその製造方法及び二次電池の負極 | |
JP6318859B2 (ja) | 銅含有シリコン材料及びその製造方法と負極活物質及び二次電池 | |
JP5660403B2 (ja) | 負極活物質とその製造方法及び蓄電装置 | |
JP6176510B2 (ja) | シリコン材料及び二次電池の負極 | |
JP5858297B2 (ja) | 負極活物質及び蓄電装置 | |
JP6011313B2 (ja) | 負極活物質とその製造方法及び蓄電装置 | |
JP6065678B2 (ja) | 負極活物質とその製造方法及び蓄電装置 | |
JP5534368B2 (ja) | 負極活物質及び蓄電装置 | |
JP6176511B2 (ja) | シリコン材料及び二次電池の負極 | |
JP5737447B2 (ja) | 銅含有層状ポリシランと負極活物質及び蓄電装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A524 | Written submission of copy of amendment under article 19 pct |
Free format text: JAPANESE INTERMEDIATE CODE: A527 Effective date: 20160930 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160930 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170615 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170628 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 6176511 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |