JP2017195083A - Negative electrode active material for nonaqueous electrolyte secondary battery, and method for manufacturing the same - Google Patents
Negative electrode active material for nonaqueous electrolyte secondary battery, and method for manufacturing the same Download PDFInfo
- Publication number
- JP2017195083A JP2017195083A JP2016084457A JP2016084457A JP2017195083A JP 2017195083 A JP2017195083 A JP 2017195083A JP 2016084457 A JP2016084457 A JP 2016084457A JP 2016084457 A JP2016084457 A JP 2016084457A JP 2017195083 A JP2017195083 A JP 2017195083A
- Authority
- JP
- Japan
- Prior art keywords
- group
- negative electrode
- alkali metal
- active material
- secondary battery
- 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
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 58
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 118
- 239000010703 silicon Substances 0.000 claims abstract description 111
- -1 alkali metal salt Chemical class 0.000 claims abstract description 99
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 62
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 44
- 150000001340 alkali metals Chemical class 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
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- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- ZPPPLBXXTCVBNC-ZVGUSBNCSA-M lithium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Li+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O ZPPPLBXXTCVBNC-ZVGUSBNCSA-M 0.000 description 1
- IOEDDFFKYCBADJ-UHFFFAOYSA-M lithium;4-methylbenzenesulfonate Chemical compound [Li+].CC1=CC=C(S([O-])(=O)=O)C=C1 IOEDDFFKYCBADJ-UHFFFAOYSA-M 0.000 description 1
- VIDXETATLKBUBY-UHFFFAOYSA-M lithium;benzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC=C1 VIDXETATLKBUBY-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 description 1
- AXMOZGKEVIBBCF-UHFFFAOYSA-M lithium;propanoate Chemical compound [Li+].CCC([O-])=O AXMOZGKEVIBBCF-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001749 primary amide group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical compound [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- QLUMLEDLZDMGDW-UHFFFAOYSA-N sodium;1h-naphthalen-1-ide Chemical compound [Na+].[C-]1=CC=CC2=CC=CC=C21 QLUMLEDLZDMGDW-UHFFFAOYSA-N 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical compound [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水電解質二次電池の負極活物質として好適なアルカリ金属塩含有シリコンオキシカーバイド及びその製造方法に関する。 The present invention relates to an alkali metal salt-containing silicon oxycarbide suitable as a negative electrode active material for a nonaqueous electrolyte secondary battery and a method for producing the same.
近年の携帯型電子機器の小型化、高性能化に伴い、これらに搭載されているリチウムイオン二次電池の高容量化が希求されている。リチウムイオン二次電池の高容量化手段として、現在負極活物質として使用されている黒鉛よりも高容量な珪素、ゲルマニウム、錫およびそれらの金属酸化物、合金化物、金属オキシカーバイドを負極活物質に使用する検討がなされている。中でも、珪素及び酸化珪素（ＳｉＯ）は高容量を有することから、次世代の負極活物質として注目されている。しかしながら、珪素及び酸化珪素はリチウム吸蔵時の体積膨張率が高いために充放電による劣化が大きく、サイクル特性が不十分である。このように、サイクル特性と高容量を兼ね備えた活物質が求められている中で、珪素や酸化珪素と比較して容量は高くはないが、リチウム吸蔵による体積膨張率が低く抑えられ、安定したサイクル特性を示すシリコンオキシカーバイド（ＳｉＯＣ）が注目されている（特許文献１）。 With the recent reduction in size and performance of portable electronic devices, there is a demand for higher capacity of lithium ion secondary batteries mounted on them. As a means for increasing the capacity of lithium ion secondary batteries, silicon, germanium, tin, and their metal oxides, alloyed products, and metal oxycarbides having higher capacities than graphite currently used as the negative electrode active material are used as the negative electrode active material. Considered to use. Among these, silicon and silicon oxide (SiO) are attracting attention as next-generation negative electrode active materials because of their high capacity. However, since silicon and silicon oxide have a high volume expansion coefficient during occlusion of lithium, deterioration due to charge / discharge is large, and cycle characteristics are insufficient. Thus, while an active material having both cycle characteristics and high capacity is demanded, the capacity is not high compared to silicon and silicon oxide, but the volume expansion coefficient due to lithium occlusion is kept low and stable. Silicon oxycarbide (SiOC) exhibiting cycle characteristics has attracted attention (Patent Document 1).
一方、シリコンオキシカーバイドは初回クーロン効率が低く、実用化の大きな障害となっている。この初回クーロン効率を改善するために、活物質に予めリチウムを添加するリチウムドープという技術が検討されている。この技術をシリコンオキシカーバイドに用いることで、初回クーロン効率が改善することが知られている（特許文献２）。しかしながら、従来技術で作製されるリチウムドープされたシリコンオキシカーバイドは、物質中に反応性の高いリチウムが残存するため、水や空気中の酸素とリチウムが容易に反応してしまう。そのため、大気中での取り扱いができず、また、負極製造プロセスで一般的に用いられる水系バインダーが使用できないため、実用化場面で問題がある。 On the other hand, silicon oxycarbide has a low initial coulomb efficiency and is a major obstacle to practical use. In order to improve the initial Coulomb efficiency, a technique called lithium doping in which lithium is added to the active material in advance has been studied. It is known that the initial coulomb efficiency is improved by using this technology for silicon oxycarbide (Patent Document 2). However, lithium-doped silicon oxycarbide produced by the prior art has a high reactivity of lithium remaining in the substance, so that oxygen in water or air easily reacts with lithium. For this reason, it cannot be handled in the atmosphere, and a water-based binder generally used in the negative electrode manufacturing process cannot be used.
上記実情を鑑み、本発明が解決しようとする課題は、高い容量、優れた初回クーロン効率を有し、かつ、大気中での取り扱いが可能な非水電解質二次電池負極の活物質として好適な材料を提供することにあり、更には、該材料の製造方法、該活物質を用いた負極、及び該負極を有する非水電解質二次電池を提供することにある。 In view of the above circumstances, the problem to be solved by the present invention is suitable as an active material for a negative electrode of a non-aqueous electrolyte secondary battery that has a high capacity, excellent initial Coulomb efficiency, and can be handled in the air. The object is to provide a material, and further to provide a method for producing the material, a negative electrode using the active material, and a non-aqueous electrolyte secondary battery having the negative electrode.
本発明者らは上記課題を解決すべく、リチウムドープされたシリコンオキシカーバイド中に含まれる不可逆なリチウム吸蔵サイトの存在に注目して鋭意検討を重ねた結果、この不可逆なリチウム吸蔵サイトを無くすことで、大気中での取扱いに問題がなく、水系バインダーも採用できるなどの実用性が高い負極活物質を得るための材料を提供することができ、かつ、該材料を負極活物質として用いた場合に、リチウムドープ技術で得られた活物質を用いた場合と同等の優れた初回クーロン効率が得られることを見出し、本発明を完成させた。 In order to solve the above-mentioned problems, the present inventors made extensive studies focusing on the existence of an irreversible lithium storage site contained in lithium-doped silicon oxycarbide, and as a result, eliminated the irreversible lithium storage site. In the case where a material for obtaining a negative electrode active material having high practicality such as no problem in handling in the air and the adoption of an aqueous binder can be provided, and the material is used as a negative electrode active material In addition, the inventors have found that excellent initial Coulomb efficiency equivalent to that obtained when an active material obtained by a lithium doping technique is used can be obtained.
本発明は、シリコンオキシカーバイドとアルカリ金属塩とを含有することを特徴とする非水電解質二次電池用負極活物質を提供する。 The present invention provides a negative electrode active material for a non-aqueous electrolyte secondary battery comprising silicon oxycarbide and an alkali metal salt.
また、本発明は、該非水電解質二次電池用負極活物質の製造方法を提供する。 Moreover, this invention provides the manufacturing method of this negative electrode active material for nonaqueous electrolyte secondary batteries.
さらに、該非水電解質二次電池用負極活物質を用いた非水電解質二次電池負極、該負極を有する非水電解質二次電池を提供する。 Furthermore, a nonaqueous electrolyte secondary battery negative electrode using the negative electrode active material for a nonaqueous electrolyte secondary battery and a nonaqueous electrolyte secondary battery having the negative electrode are provided.
すなわち本発明は、以下の項１〜項１２に関する。
項１．シリコンオキシカーバイドとアルカリ金属塩とを含有することを特徴とする非水電解質二次電池用負極活物質。
項２．
前記シリコンオキシカーバイドが、ＳｉＯｙＣｚ（０＜ｙ＜３、０＜ｚ＜１０）の組成式で表される項１に記載の非水電解質二次電池用負極活物質。
項３．
前記アルカリ金属塩のアルカリ金属が、リチウム又はナトリウムであることを特徴とする項１に記載の非水電解質二次電池用負極活物質。
項４．
アルカリ金属塩の含有量が、シリコンオキシカーバイド中の珪素原子（Ｓｉ）とアルカリ金属塩中のアルカリ金属原子（ＭＡ）の比が０＜ＭＡ／Ｓｉ＜１０の範囲で表せる量であることを特徴とする項１に記載の非水電解質二次電池用負極活物質。
項５．
項１〜項４に記載の非水電解質二次電池用負極活物質とバインダーとを含むことを特徴とする非水電解質二次電池用負極。
項６．
項５に記載の非水電解質二次電池用負極を有することを特徴とする非水電解質二次電池。
項７．
シリコンオキシカーバイドと、アルカリ金属及びアルカリ金属化合物からなる群より選ばれる少なくとも１種を含むアルカリ金属源とを混合し、アルカリ金属含有シリコンオキシカーバイドを得る工程（１）と、
工程（１）により得られたアルカリ金属含有シリコンオキシカーバイドを、アルコール、水及び酸性溶液からなる群より選ばれる少なくとも１種で洗浄処理する工程（２）を含むことを特徴とする非水電解質二次電池用負極活物質の製造方法。
項８．
前記アルカリ金属源が、リチウム、ナトリウム、リチウム金属化合物及びナトリウム金属化合物からなる群より選ばれる少なくとも１種であることを特徴とする項７に記載の非水電解質二次電池用負極活物質の製造方法。
項９．
前記アルコールが、２００℃以下の沸点を有するアルコールである項７に記載の非水電解質二次電池用負極活物質の製造方法。
項１０．
前記酸性溶液が、無機酸、スルホン酸及びカルボン酸からなる群より選ばれる少なくとも１種の溶液である項７に記載の非水電解質二次電池用負極活物質の製造方法。
項１１．
シリコンオキシカーバイドと、アルカリ金属及びアルカリ金属化合物からなる群より選ばれる少なくとも１種を含むアルカリ金属源とを混合し、アルカリ金属含有シリコンオキシカーバイドを得る工程（１）と、
工程（１）で得られたアルカリ金属含有シリコンオキシカーバイドを酸素雰囲気又は窒素雰囲気中で加熱する工程（２）を含むことを特徴とする非水電解質二次電池用負極活物質の製造方法。
項１２．
前記アルカリ金属源が、リチウム、ナトリウム、リチウム金属化合物及びナトリウム金属化合物からなる群より選ばれる少なくとも１種であることを特徴とする項１１に記載の非水電解質二次電池用負極活物質の製造方法。
That is, the present invention relates to the following items 1 to 12.
Item 1. A negative electrode active material for a nonaqueous electrolyte secondary battery, comprising silicon oxycarbide and an alkali metal salt.
Item 2.
Item 2. The negative electrode active material for a nonaqueous electrolyte secondary battery according to Item 1, wherein the silicon oxycarbide is represented by a composition formula of SiOyCz (0 <y <3, 0 <z <10).
Item 3.
The negative electrode active material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the alkali metal of the alkali metal salt is lithium or sodium.
Item 4.
The content of the alkali metal salt is such that the ratio of the silicon atom (Si) in the silicon oxycarbide to the alkali metal atom (MA) in the alkali metal salt can be expressed in a range of 0 <MA / Si <10. Item 2. The negative electrode active material for a nonaqueous electrolyte secondary battery according to Item 1.
Item 5.
Item 5. A negative electrode for a non-aqueous electrolyte secondary battery comprising the negative electrode active material for a non-aqueous electrolyte secondary battery according to Item 1 to Item 4 and a binder.
Item 6.
A nonaqueous electrolyte secondary battery comprising the negative electrode for a nonaqueous electrolyte secondary battery according to Item 5.
Item 7.
Mixing silicon oxycarbide with an alkali metal source containing at least one selected from the group consisting of alkali metals and alkali metal compounds to obtain an alkali metal-containing silicon oxycarbide (1);
A non-aqueous electrolyte 2 comprising a step (2) of washing the alkali metal-containing silicon oxycarbide obtained in the step (1) with at least one selected from the group consisting of alcohol, water and an acidic solution. The manufacturing method of the negative electrode active material for secondary batteries.
Item 8.
The production of a negative electrode active material for a nonaqueous electrolyte secondary battery according to claim 7, wherein the alkali metal source is at least one selected from the group consisting of lithium, sodium, a lithium metal compound, and a sodium metal compound. Method.
Item 9.
Item 8. The method for producing a negative electrode active material for a non-aqueous electrolyte secondary battery according to Item 7, wherein the alcohol is an alcohol having a boiling point of 200 ° C or lower.
Item 10.
Item 8. The method for producing a negative electrode active material for a nonaqueous electrolyte secondary battery according to Item 7, wherein the acidic solution is at least one solution selected from the group consisting of inorganic acids, sulfonic acids, and carboxylic acids.
Item 11.
Mixing silicon oxycarbide with an alkali metal source containing at least one selected from the group consisting of alkali metals and alkali metal compounds to obtain an alkali metal-containing silicon oxycarbide (1);
A method for producing a negative electrode active material for a nonaqueous electrolyte secondary battery, comprising a step (2) of heating the alkali metal-containing silicon oxycarbide obtained in the step (1) in an oxygen atmosphere or a nitrogen atmosphere.
Item 12.
12. The production of a negative electrode active material for a nonaqueous electrolyte secondary battery according to claim 11, wherein the alkali metal source is at least one selected from the group consisting of lithium, sodium, a lithium metal compound, and a sodium metal compound. Method.
本発明のシリコンオキシカーバイドとアルカリ金属塩とを含有する非水電解質二次電池負極用活物質は、安全性が高く、大気中での取扱いが容易であることから、電池製造時の作業性が改善され、また、負極製造に一般に用いられる水性バインダーも採用可能である。さらに、該活物質は、優れた電池特性を発揮する。具体的には、高い容量を有し、かつ、優れた初回クーロン効率を有する。このように本発明は、安全性を確保しつつ、従来知られたリチウムドープ手法と同等の電池特性を達成可能な格別顕著な効果を奏する。また、本発明によれば、上記のような優れた特性を有するシリコンオキシカーバイドとアルカリ金属塩とを含有する非水電解質二次電池負極用活物質を簡便に製造することができる。 The active material for a non-aqueous electrolyte secondary battery negative electrode containing silicon oxycarbide and an alkali metal salt of the present invention has high safety and is easy to handle in the air, so that workability during battery production is improved. It is also possible to employ an aqueous binder that has been improved and is generally used in the production of negative electrodes. Furthermore, the active material exhibits excellent battery characteristics. Specifically, it has a high capacity and excellent initial Coulomb efficiency. As described above, the present invention has a particularly remarkable effect capable of achieving battery characteristics equivalent to those of a conventionally known lithium doping method while ensuring safety. Moreover, according to this invention, the active material for nonaqueous electrolyte secondary battery negative electrodes containing the silicon oxycarbide and alkali metal salt which have the above outstanding characteristics can be manufactured simply.
以下、詳細に本発明を説明する。 Hereinafter, the present invention will be described in detail.
本発明は、シリコンオキシカーバイドとアルカリ金属塩とを含有することを特徴とする非水電解質二次電池用負極活物質である。 The present invention is a negative electrode active material for a non-aqueous electrolyte secondary battery comprising silicon oxycarbide and an alkali metal salt.
まず、本発明においた用いた技術用語を説明する。
＜シリコンオキシカーバイド＞
本発明に用いるシリコンオキシカーバイド（ＳｉＯＣとも表記される）は、珪素含有複合樹脂を熱分解することで得られる。このようにして得られるシリコンオキシカーバイドは珪素、炭素、酸素を広範囲の組み合わせ割合で含む。シリコンオキシカーバイドの組成はＳｉＯｙＣｚとあらわすことができ、ＳｉＯｙＣｚ（０＜ｙ＜３、０＜ｚ＜１０）の組成式で表されるシリコンオキシカーバイドであることが好ましく、ＳｉＯｙＣｚ（０＜ｙ＜２、０＜ｚ＜１０）の組成式で表されるシリコンオキシカーバイドであることがさらに好ましい。
First, technical terms used in the present invention will be described.
<Silicon oxycarbide>
Silicon oxycarbide (also expressed as SiOC) used in the present invention can be obtained by thermally decomposing a silicon-containing composite resin. The silicon oxycarbide thus obtained contains silicon, carbon, and oxygen in a wide range of combination ratios. The composition of silicon oxycarbide can be expressed as SiOyCz, and is preferably silicon oxycarbide represented by a composition formula of SiOyCz (0 <y <3, 0 <z <10), and SiOyCz (0 <y <2 Further, silicon oxycarbide represented by a composition formula of 0 <z <10) is more preferable.
ここで、珪素含有複合樹脂とは、ポリカルボシラン、ポリシラザン、ポリシラン及びポリシロキサンセグメントを少なくとも１つ含む樹脂である。 Here, the silicon-containing composite resin is a resin containing at least one of polycarbosilane, polysilazane, polysilane, and polysiloxane segments.
本発明に用いるシリコンオキシカーバイドの製造方法として、例えば、次のような方法が挙げられる。 Examples of the method for producing silicon oxycarbide used in the present invention include the following methods.
後記する実施例では、シラノール基および／または加水分解性シリル基、並びにポリシロキサンセグメント（ａ１）と、該ポリシロキサンセグメント（ａ１）以外の重合体セグメント（ａ２）とを有する珪素含有複合樹脂（Ａ）を熱分解して得られるシリコンオキシカーバイドを使用している。前記ポリシロキサンセグメント（ａ１）が、下記一般式（Ｓ−２）および／または下記一般式（Ｓ−３）で表される構造単位を有するポリシロキサンセグメントであるものを用いることが好ましい。 In the examples described later, a silicon-containing composite resin (A) having a silanol group and / or a hydrolyzable silyl group, a polysiloxane segment (a1), and a polymer segment (a2) other than the polysiloxane segment (a1). ) Is obtained by thermal decomposition of silicon oxycarbide. The polysiloxane segment (a1) is preferably a polysiloxane segment having a structural unit represented by the following general formula (S-2) and / or the following general formula (S-3).
（前記一般式（Ｓ−２）及び（Ｓ−３）中、Ｒ３、Ｒ４及びＲ５は、それぞれ独立して炭素原子数が１〜６のアルキル基、炭素原子数が３〜８のシクロアルキル基、アリール基または炭素原子数が７〜１２のアラルキル基を示す。）
この場合、前記ポリシロキサンセグメント（ａ１）の含有率が、前記珪素含有複合樹脂（Ａ）に対して１０〜９５質量％であることが好ましい。また、前記重合体セグメント（ａ２）が、ビニル重合体セグメントであることが好ましい。さらに、前記珪素含有複合樹脂（Ａ）が、ポリシロキサンセグメント（ａ１）と重合体セグメント（ａ２）とが下記の構造式（Ｓ−５）で示される構造で結合した複合樹脂であることが好ましい。
(In the general formulas (S-2) and (S-3), R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms and 3 to 8 carbon atoms. A cycloalkyl group, an aryl group, or an aralkyl group having 7 to 12 carbon atoms.)
In this case, it is preferable that the content rate of the said polysiloxane segment (a1) is 10-95 mass% with respect to the said silicon containing composite resin (A). Moreover, it is preferable that the said polymer segment (a2) is a vinyl polymer segment. Furthermore, it is preferable that the silicon-containing composite resin (A) is a composite resin in which a polysiloxane segment (a1) and a polymer segment (a2) are bonded with a structure represented by the following structural formula (S-5). .
（式中、炭素原子は重合体セグメント（ａ２）を構成する炭素原子であり、２個の珪素原子はポリシロキサンセグメント（ａ１）を構成する珪素原子である） (In the formula, carbon atoms are carbon atoms constituting the polymer segment (a2), and two silicon atoms are silicon atoms constituting the polysiloxane segment (a1)).
ここで言う珪素含有複合樹脂（Ａ）としては、例えば、前記ポリシロキサンセグメント（ａ１）が前記重合体セグメント（ａ２）の側鎖に化学的に結合したグラフト構造を有する複合樹脂、前記重合体セグメント（ａ２）の末端に前記ポリシロキサンセグメント（ａ１）が化学的に結合したブロック構造を有する複合樹脂等が挙げられる。 Examples of the silicon-containing composite resin (A) herein include a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded to a side chain of the polymer segment (a2), and the polymer segment. Examples thereof include a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded to the terminal of (a2).
前記珪素含有複合樹脂（Ａ）が有するポリシロキサンセグメント（ａ１）は、該ポリシロキサンセグメント（ａ１）中に重合性二重結合など加熱により反応が可能な官能基を有していてもよい。熱分解前に珪素含有複合樹脂（Ａ）を加熱処理することにより、架橋反応が進行し、固体状とすることにより、熱分解処理を容易に行うことができる。 The polysiloxane segment (a1) contained in the silicon-containing composite resin (A) may have a functional group capable of reacting by heating such as a polymerizable double bond in the polysiloxane segment (a1). By heat-treating the silicon-containing composite resin (A) before pyrolysis, the cross-linking reaction proceeds, and the pyrolysis treatment can be easily performed by making it into a solid state.
前記重合性二重結合としては、例えば、ビニル基や（メタ）アクリロイル基等が挙げられる。重合性二重結合は、ポリシロキサンセグメント（ａ１）中に２つ以上存在することが好ましく３〜２００個存在することがより好ましく、３〜５０個存在することが更に好ましい。また、珪素含有複合樹脂（Ａ）として重合性二重結合が２個以上存在する複合樹脂を使用することによって、架橋反応が容易に進行させることができる。 Examples of the polymerizable double bond include a vinyl group and a (meth) acryloyl group. Two or more polymerizable double bonds are preferably present in the polysiloxane segment (a1), more preferably 3 to 200, and even more preferably 3 to 50. Further, by using a composite resin having two or more polymerizable double bonds as the silicon-containing composite resin (A), the cross-linking reaction can easily proceed.
前記ポリシロキサンセグメント（ａ１）は、シラノール基および／または加水分解性シリル基を有している。前記熱硬化反応と並行して、シラノール基中の水酸基や加水分解性シリル基中の前記加水分解性基の間で加水分解縮合反応が進行することで、得られる塗膜のポリシロキサン構造の架橋反応が進行し、固体状の珪素含有複合樹脂（Ａ）を得ることができる。 The polysiloxane segment (a1) has a silanol group and / or a hydrolyzable silyl group. In parallel with the thermosetting reaction, the hydrolysis and condensation reaction proceeds between the hydroxyl group in the silanol group and the hydrolyzable group in the hydrolyzable silyl group, thereby crosslinking the polysiloxane structure of the resulting coating film. The reaction proceeds and a solid silicon-containing composite resin (A) can be obtained.
本発明で言うシラノール基とは珪素原子に直接結合した水酸基を有する珪素含有基である。本発明で言う加水分解性シリル基とは珪素原子に直接結合した加水分解性基を有する珪素含有基であり、具体的には、例えば、下記の一般式で表される基が挙げられる。 The silanol group referred to in the present invention is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. The hydrolyzable silyl group referred to in the present invention is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specific examples include groups represented by the following general formula.
（式中、Ｒ１はアルキル基、アリール基又はアラルキル基等の１価の有機基を、Ｒ２はハロゲン原子、アルコキシ基、アシロキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基又はアルケニルオキシ基である。またｂは０〜２の整数である。） (Wherein R 1 is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, R 2 is a halogen atom, alkoxy group, acyloxy group, aryloxy group, mercapto group, amino group, amide group, amino An oxy group, an iminooxy group or an alkenyloxy group, and b is an integer of 0 to 2.)
前記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、１−メチルブチル基、２−メチルブチル基、１，２−ジメチルプロピル基、１−エチルプロピル基、ヘキシル基、イソヘシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、１，１−ジメチルブチル基、１，２−ジメチルブチル基、２，２−ジメチルブチル基、１−エチルブチル基、１，１，２−トリメチルプロピル基、１，２，２−トリメチルプロピル基、１−エチル−２−メチルプロピル基、１−エチル−１−メチルプロピル基等が挙げられる。 Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1, 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl Examples include 2-methylpropyl group and 1-ethyl-1-methylpropyl group.
前記アリール基としては、例えば、フェニル基、ナフチル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−ビニルフェニル基、３−イソプロピルフェニル基等が挙げられる。 As said aryl group, a phenyl group, a naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group etc. are mentioned, for example.
前記アラルキル基としては、例えば、ベンジル基、ジフェニルメチル基、ナフチルメチル基等が挙げられる。 Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
前記ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
前記アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、第二ブトキシ基、第三ブトキシ基等が挙げられる。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.
前記アシロキシ基としては、例えば、ホルミルオキシ、アセトキシ、プロパノイルオキシ、ブタノイルオキシ、ピバロイルオキシ、ペンタノイルオキシ、フェニルアセトキシ、アセトアセトキシ、ベンゾイルオキシ、ナフトイルオキシ等が挙げられる。 Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy, and the like.
前記アリールオキシ基としては、例えば、フェニルオキシ、ナフチルオキシ等が挙げられる。 Examples of the aryloxy group include phenyloxy and naphthyloxy.
前記アルケニルオキシ基としては、例えば、ビニルオキシ基、アリルオキシ基、１−プロペニルオキシ基、イソプロペニルオキシ基、２−ブテニルオキシ基、３−ブテニルオキシ基、２−ペテニルオキシ基、３−メチル−３−ブテニルオキシ基、２−ヘキセニルオキシ基等が挙げられる。 Examples of the alkenyloxy group include a vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2-hexenyloxy group etc. are mentioned.
前記ポリシロキサンセグメント（ａ１）が有する加水分解性シリル基中の加水分解性基としては、例えば、例えばハロゲン原子、アルコキシ基、置換アルコキシ基、アシロキシ基、フェノキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基、アルケニルオキシ基等が挙げられ、これらの基が加水分解されることにより加水分解性シリル基はシラノール基となる。そして、このシラノール基の水酸基が脱水縮合に用いられ、ポリシロキサンセグメント（ａ１）部分の架橋反応が進行する。 Examples of the hydrolyzable group in the hydrolyzable silyl group of the polysiloxane segment (a1) include, for example, a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, and an amide group. , Aminooxy group, iminooxy group, alkenyloxy group and the like, and hydrolyzable silyl group becomes silanol group by hydrolyzing these groups. And the hydroxyl group of this silanol group is used for dehydration condensation, and the crosslinking reaction of a polysiloxane segment (a1) part advances.
前記ポリシロキサンセグメント（ａ１）は、下記一般式（Ｓ−２）および／または下記一般式（Ｓ−３）で示される構造単位を有するポリシロキサンセグメントが好ましい。下記一般式（Ｓ−２）および／または下記一般式（Ｓ−３）で示される構造単位を有するポリシロキサンセグメントは三次元網目状のポリシロキサン構造を有する。従って、複合樹脂としてこのようなポリシロキサンセグメントを有する珪素含有複合樹脂（Ａ）を用い、熱分解することによりシリコンオキシカーバイドを得ることが可能となる。 The polysiloxane segment (a1) is preferably a polysiloxane segment having a structural unit represented by the following general formula (S-2) and / or the following general formula (S-3). The polysiloxane segment having a structural unit represented by the following general formula (S-2) and / or the following general formula (S-3) has a three-dimensional network polysiloxane structure. Therefore, silicon oxycarbide can be obtained by using the silicon-containing composite resin (A) having such a polysiloxane segment as the composite resin and thermally decomposing it.
（前記一般式（Ｓ−２）及び（Ｓ−３）中、Ｒ３、Ｒ４及びＲ５は、それぞれ独立して炭素原子数が１〜６のアルキル基、炭素原子数が３〜８のシクロアルキル基、アリール基または炭素原子数が７〜１２のアラルキル基を示す。） (In the general formulas (S-2) and (S-3), R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms and 3 to 8 carbon atoms. A cycloalkyl group, an aryl group, or an aralkyl group having 7 to 12 carbon atoms.)
前記炭素原子数が１〜６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチ基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、１−メチルブチル基、２−メチルブチル基、１，２−ジメチルプロピル基、１−エチルプロピル基、ヘキシル基、イソヘシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、１，１−ジメチルブチル基、１，２−ジメチルブチル基、２，２−ジメチルブチル基、１−エチルブチル基、１，１，２−トリメチルプロピル基、１，２，２−トリメチルプロピル基、１−エチル−２−メチルプロピル基、１−エチル−１−メチルプロピル基等が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-buty group, pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2 -A trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, etc. are mentioned.
前記炭素原子数が３〜８のシクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。 Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
前記アリール基としては、例えば、フェニル基、ナフチル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−ビニルフェニル基、３−イソプロピルフェニル基等が挙げられる。 As said aryl group, a phenyl group, a naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-vinylphenyl group, 3-isopropylphenyl group etc. are mentioned, for example.
前記炭素原子数が７〜１２のアラルキル基としては、例えば、ベンジル基、ジフェニルメチル基、ナフチルメチル基等が挙げられる。 Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
前記一般式（Ｓ−２）および／または下記一般式（Ｓ−３）で示される構造単位を有するポリシロキサンセグメントとしては、例えば以下の構造を有するもの等が挙げられる。 Examples of the polysiloxane segment having a structural unit represented by the general formula (S-2) and / or the following general formula (S-3) include those having the following structure.
前記珪素含有複合樹脂（Ａ）が有するポリシロキサンセグメント（ａ１）以外の重合体セグメント（ａ２）としては、例えば、アクリル重合体、フルオロオレフィン重合体、ビニルエステル重合体、芳香族系ビニル重合体、ポリオレフィン重合体等のビニル重合体セグメントや、ポリウレタン重合体セグメント、ポリエステル重合体セグメント、ポリエーテル重合体セグメント等の重合体セグメント等が挙げられる。中でも、ビニル重合体セグメントが好ましい。 Examples of the polymer segment (a2) other than the polysiloxane segment (a1) of the silicon-containing composite resin (A) include an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, Examples thereof include vinyl polymer segments such as polyolefin polymers, polymer segments such as polyurethane polymer segments, polyester polymer segments, and polyether polymer segments. Among these, a vinyl polymer segment is preferable.
前記重合体セグメント（ａ２）は、本発明の効果を阻害しない範囲で、必要に応じて各種官能基を有していても良い。かかる官能基としては、例えばカルボキシル基、ブロックされたカルボキシル基、カルボン酸無水基、３級アミノ基、水酸基、ブロックされた水酸基、シクロカーボネート基、エポキシ基、カルボニル基、１級アミド基、２級アミド、カーバメート基、下記の構造式（Ｓ−４）で表される官能基等を使用することができる。 The polymer segment (a2) may have various functional groups as necessary as long as the effects of the present invention are not impaired. Examples of such functional groups include carboxyl groups, blocked carboxyl groups, carboxylic anhydride groups, tertiary amino groups, hydroxyl groups, blocked hydroxyl groups, cyclocarbonate groups, epoxy groups, carbonyl groups, primary amide groups, and secondary groups. Amides, carbamate groups, functional groups represented by the following structural formula (S-4), and the like can be used.
また、前記重合体セグメント（ａ２）は、ビニル基、（メタ）アクリロイル基等の重合性二重結合を有していても良い。 The polymer segment (a2) may have a polymerizable double bond such as a vinyl group or a (meth) acryloyl group.
本発明で用いる珪素含有複合樹脂（Ａ）としては、ポリシロキサンセグメント（ａ１）と重合体セグメント（ａ２）とが下記構造式（Ｓ−５）で表される構造で結合した複合樹脂や下記構造式（Ｓ−６）で表される構造で結合した複合樹脂等が挙げられる。 Examples of the silicon-containing composite resin (A) used in the present invention include a composite resin in which a polysiloxane segment (a1) and a polymer segment (a2) are bonded in a structure represented by the following structural formula (S-5), and the following structure. Examples thereof include a composite resin bonded with a structure represented by the formula (S-6).
構造式（Ｓ−５）中、炭素原子は重合体セグメント（ａ２）を構成する炭素原子であり、２個の珪素原子はポリシロキサンセグメント（ａ１）を構成する珪素原子である） In the structural formula (S-5), carbon atoms are carbon atoms constituting the polymer segment (a2), and two silicon atoms are silicon atoms constituting the polysiloxane segment (a1))
構造式（Ｓ−６）中、炭素原子は重合体セグメント（ａ２）を構成する炭素原子であり、珪素原子はポリシロキサンセグメント（ａ１）を構成する珪素原子である） In the structural formula (S-6), the carbon atom is a carbon atom constituting the polymer segment (a2), and the silicon atom is a silicon atom constituting the polysiloxane segment (a1))
本発明で用いる珪素含有複合樹脂（Ａ）は、公知の方法で製造できるが、なかでも下記（１）〜（３）に示す方法で製造することが好ましい。但し、これらに限定されるものではない。 The silicon-containing composite resin (A) used in the present invention can be produced by a known method, but among them, it is preferably produced by the methods shown in the following (1) to (3). However, it is not limited to these.
（１）前記重合体セグメント（ａ２）の原料として、シラノール基および／または加水分解性シリル基を含有する重合体セグメント（ａ２−１）を予め調製しておき、この重合体セグメント（ａ２−１）と、シラノール基および／または加水分解性シリル基、並びに重合性二重結合を併有するシラン化合物を含有するシラン化合物とを混合し、加水分解縮合反応を行う方法。 (1) As a raw material of the polymer segment (a2), a polymer segment (a2-1) containing a silanol group and / or a hydrolyzable silyl group is prepared in advance, and this polymer segment (a2-1) is prepared. ) And a silane compound containing a silanol group and / or a hydrolyzable silyl group and a silane compound having a polymerizable double bond, and carrying out a hydrolysis condensation reaction.
（２）前記重合体セグメント（ａ２）の原料として、シラノール基および／または加水分解性シリル基を含有する重合体セグメント（ａ２−１）を予め調製する。また、シラノール基および／または加水分解性シリル基、並びに重合性二重結合を併有するシラン化合物を含有するシラン化合物を加水分解縮合反応してポリシロキサン（ａ１−１）も予め調製しておく。そして、重合体セグメント（ａ２−１）とポリシロキサン（ａ１−１）とを混合し、加水分解縮合反応を行う方法。 (2) As a raw material of the polymer segment (a2), a polymer segment (a2-1) containing a silanol group and / or a hydrolyzable silyl group is prepared in advance. Also, polysiloxane (a1-1) is prepared in advance by hydrolytic condensation reaction of a silane compound containing a silanol group and / or a hydrolyzable silyl group and a silane compound having both polymerizable double bonds. And the polymer segment (a2-1) and polysiloxane (a1-1) are mixed, and the method of performing a hydrolytic condensation reaction.
（３）前記重合体セグメント（ａ２−１）と、シラノール基および／または加水分解性シリル基、並びに重合性二重結合を併有するシラン化合物を含有するシラン化合物と、ポリシロキサン（ａ１−１）とを混合し、加水分解縮合反応を行う方法。 (3) The polymer segment (a2-1), a silane compound containing a silanol group and / or a hydrolyzable silyl group, and a silane compound having both polymerizable double bonds, and a polysiloxane (a1-1) And performing a hydrolytic condensation reaction.
前記シリコンオキシカーバイドは、さらに黒鉛性粒子を含んでも良い。黒鉛性粒子（黒鉛性物質）は、人造黒鉛および天然黒鉛に大別されるが、電池容量と純度の面から、人造黒鉛であることが好ましい。 The silicon oxycarbide may further contain graphitic particles. Graphite particles (graphitic substances) are roughly classified into artificial graphite and natural graphite, but artificial graphite is preferable from the viewpoint of battery capacity and purity.
前記シリコンオキシカーバイドは、さらに珪素粒子を含んでも良い。珪素は、工業用として市販されている比較的低純度のものから、電子部品用材料として使用されている高純度のものまでいずれも使用することができる。珪素粒子の体積平均粒子径は０．０１μｍ〜２０μｍが好ましく、より好ましくは０．０５μｍ〜１０μｍであり、さらに好ましくは、０．１μｍ〜５μｍの粒子であり、特に好ましくは０．１μｍ〜１μｍである。珪素粒子の体積平均粒子径が０．０１μｍ〜２０μｍの範囲内であると、高い初回充放電効率及び優れたサイクル特性を示すリチウムイオン二次電池用負極材として使用できる。体積平均粒子径が０．０１μｍ以上であることで、珪素粒子の生産性及び取り扱い性が向上する。 The silicon oxycarbide may further contain silicon particles. Silicon can be used from a relatively low purity commercially available for industrial use to a high purity used as a material for electronic parts. The volume average particle diameter of the silicon particles is preferably 0.01 μm to 20 μm, more preferably 0.05 μm to 10 μm, still more preferably 0.1 μm to 5 μm, and particularly preferably 0.1 μm to 1 μm. is there. When the volume average particle diameter of the silicon particles is in the range of 0.01 μm to 20 μm, it can be used as a negative electrode material for a lithium ion secondary battery exhibiting high initial charge / discharge efficiency and excellent cycle characteristics. When the volume average particle diameter is 0.01 μm or more, the productivity and handleability of silicon particles are improved.
熱分解は公知慣用の方法で行うことができ、特に制限はないが、例えば、不活性のガス雰囲気下で、１分当たり５℃で昇温を行い、以下の温度で熱分解を行うことができる。 Thermal decomposition can be performed by a known and commonly used method, and is not particularly limited. For example, the temperature can be increased at 5 ° C. per minute in an inert gas atmosphere, and the thermal decomposition can be performed at the following temperature. it can.
熱分解の温度に制限はないが、好ましくは、５００〜１５００℃、より好ましくは、６００〜１５００℃、特に好ましくは６００〜１３００℃の温度を挙げることができる。 Although there is no restriction | limiting in the temperature of thermal decomposition, Preferably, the temperature of 500-1500 degreeC, More preferably, it is 600-1500 degreeC, Especially preferably, the temperature of 600-1300 degreeC can be mentioned.
不活性ガスとしては、窒素、ヘリウム、アルゴンなどが例示される。なお、この不活性ガス中に、水素ガス等の還元性ガスを含んでもよい。 Examples of the inert gas include nitrogen, helium, and argon. The inert gas may contain a reducing gas such as hydrogen gas.
最終到達温度１５００℃以上になると、炭化珪素の成長を助長するため好ましくない。一方、最終到達温度が上記範囲の下限より低いと、有機成分の炭化が不十分となる。なお、この熱分解工程は二段階以上で行なっても良い。すなわち、第一段階において、最終到達温度より低温で一定時間熱分解を行い、再度昇温し熱分解することができる。 A final ultimate temperature of 1500 ° C. or higher is not preferable because it promotes the growth of silicon carbide. On the other hand, when the final temperature reached is lower than the lower limit of the above range, carbonization of the organic component becomes insufficient. In addition, you may perform this thermal decomposition process in two steps or more. That is, in the first stage, thermal decomposition can be performed for a certain period of time at a temperature lower than the final temperature, and the temperature can be increased again to perform thermal decomposition.
前記加熱処理は、固定床又は流動床方式の炭化炉で行うことができ、所定温度へ昇温できる機能を有する炉であれば、炭化炉の加熱方式及び種類は特に限定されない。炭化炉としては、例えば、リードハンマー炉、トンネル炉、単独炉等が挙げられる。 The heat treatment can be performed in a fixed bed or fluidized bed type carbonization furnace, and the heating method and type of the carbonization furnace are not particularly limited as long as the furnace has a function of raising the temperature to a predetermined temperature. Examples of the carbonizing furnace include a lead hammer furnace, a tunnel furnace, and a single furnace.
本発明の負極活物質が含有するアルカリ金属塩の具体例としては、ケイ酸塩、炭酸塩、水酸化物、ハロゲン化物、硫酸塩、硝酸塩、リン酸塩、スルホン酸塩、カルボン酸塩、アルコキシドなどが挙げられる。ケイ酸塩の具体例として、オルトケイ酸リチウム、メタケイ酸リチウム、オルトケイ酸ナトリウム、メタケイ酸ナトリウム、オルトケイ酸カリウム、メタケイ酸カリウムなどが挙げられる。炭酸塩の具体例として、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウムなどが挙げられる。水酸化物の具体例として、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化ルビジウム、水酸化セシウムなどが挙げられる。ハロゲン化物の具体例として、フッ化リチウム、フッ化ナトリウム、フッ化カリウム、フッ化ルビジウム、フッ化セシウム、塩化リチウム、塩化ナトリウム、塩化カリウム、塩化ルビジウム、塩化セシウム、臭化リチウム、臭化ナトリウム、臭化カリウム、臭化ルビジウム、臭化セシウム、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化ルビジウム、ヨウ化セシウムなどが挙げられる。硫酸塩の具体例として、硫酸リチウム、硫酸ナトリウム、硫酸カリウム、硫酸ルビジウム、硫酸セシウムなどが挙げられる。硝酸塩の具体例として、硝酸リチウム、硝酸ナトリウム、硝酸カリウム、硝酸ルビジウム、硝酸セシウムなどが挙げられる。リン酸塩の具体例として、リン酸リチウム、リン酸ナトリウム、リン酸カリウム、リン酸ルビジウム、リン酸セシウムなどが挙げられる。スルホン酸塩の具体例として、メタンスルホン酸リチウム、メタンスルホン酸ナトリウム、ベンゼンスルホン酸リチウム、ベンゼンスルホン酸ナトリウム、ｐ−トルエンスルホン酸リチウム、ｐ−トルエンスルホン酸ナトリウム、ｐ−トルエンスルホン酸カリウムなどが挙げられる。カルボン酸塩の具体例として、ギ酸リチウム、ギ酸ナトリウム、ギ酸カリウム、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、プロピオン酸リチウム、プロピオン酸ナトリウム、プロピオン酸カリウム、安息香酸リチウム、安息香酸ナトリウム、安息香酸カリウム、シュウ酸リチウム、シュウ酸ナトリウム、シュウ酸カリウム、クエン酸リチウム、クエン酸ナトリウム、クエン酸カリウム、酒石酸リチウム、酒石酸ナトリウム、酒石酸カリウムなどがあげられる。 Specific examples of the alkali metal salt contained in the negative electrode active material of the present invention include silicate, carbonate, hydroxide, halide, sulfate, nitrate, phosphate, sulfonate, carboxylate, and alkoxide. Etc. Specific examples of the silicate include lithium orthosilicate, lithium metasilicate, sodium orthosilicate, sodium metasilicate, potassium orthosilicate, and potassium metasilicate. Specific examples of the carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate and the like. Specific examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. Specific examples of halides include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, Examples include potassium bromide, rubidium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide and the like. Specific examples of the sulfate include lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, and cesium sulfate. Specific examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, and cesium nitrate. Specific examples of the phosphate include lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, cesium phosphate and the like. Specific examples of the sulfonate include lithium methanesulfonate, sodium methanesulfonate, lithium benzenesulfonate, sodium benzenesulfonate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, and potassium p-toluenesulfonate. Can be mentioned. Specific examples of carboxylates include lithium formate, sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, potassium propionate, lithium benzoate, sodium benzoate, potassium benzoate, Examples include lithium oxalate, sodium oxalate, potassium oxalate, lithium citrate, sodium citrate, potassium citrate, lithium tartrate, sodium tartrate, potassium tartrate and the like.
含まれるアルカリ金属塩は単独でもよく、２種類以上のアルカリ金属塩でもよい。 The alkali metal salt contained may be single, and 2 or more types of alkali metal salts may be sufficient as it.
本発明の負極活物質中に含まれるアルカリ金属塩の含有量は、シリコンオキシカーバイド中の珪素原子（Ｓｉ）とアルカリ金属塩中のアルカリ金属原子（ＭＡ）の比が０＜ＭＡ／Ｓｉ＜１０の範囲となるように含有させることが好ましく、０＜ＭＡ／Ｓｉ＜２の範囲となるように含有させることがより好ましい。
＜リチウムドープ＞
本発明でリチウムドープとは金属リチウム及び/またはリチウム化合物を用いて、活物質中にリチウムを吸蔵（Ｌｉｔｈｉａｉｔｏｎ化、インターカレーション、ドープ、挿入、吸蔵、担持、合金化等種々の言葉で表現されるが、これらを総称して本発明ではドープと記載し、説明する。）させることである。
＜失活＞
本発明の製造工程において用いた用語「失活」とは、活物質中にドープしたアルカリ金属が酸化されアルカリ金属イオンの状態になることをいう。アルカリ金属イオンは塩の状態でおり、ケイ酸塩、炭酸塩、水酸化物、ハロゲン化物、硫酸塩、硝酸塩、リン酸塩、スルホン酸塩、カルボン酸塩、アルコキシドなどで存在する。シリコンオキシカーバイド中のアルカリ金属が失活しているかを確認するには、シリコンオキシカーバイドに水を加えて水素が発生しないことで確認することができる。アルカリ金属が残っている場合は、アルカリ金属と水が反応し、水素とアルカリ金属の水酸化物となる。
The content of the alkali metal salt contained in the negative electrode active material of the present invention is such that the ratio of silicon atom (Si) in silicon oxycarbide to alkali metal atom (MA) in the alkali metal salt is 0 <MA / Si <10. It is preferable to contain so that it may become the range of this, and it is more preferable to contain so that it may become the range of 0 <MA / Si <2.
<Lithium dope>
In the present invention, lithium dope is expressed in various terms such as lithium ionization, intercalation, dope, insertion, occlusion, loading, alloying, etc. using lithium metal and / or lithium compounds in the active material. However, these are collectively referred to as “dope” in the present invention.
<Deactivation>
The term “deactivation” used in the production process of the present invention means that an alkali metal doped in an active material is oxidized to be in an alkali metal ion state. Alkali metal ions are in a salt state and exist as silicates, carbonates, hydroxides, halides, sulfates, nitrates, phosphates, sulfonates, carboxylates, alkoxides, and the like. In order to confirm whether the alkali metal in silicon oxycarbide has been deactivated, it can be confirmed by adding water to silicon oxycarbide to prevent generation of hydrogen. When the alkali metal remains, the alkali metal and water react to form hydrogen and an alkali metal hydroxide.
本発明のシリコンオキシカーバイドとアルカリ金属塩とを含む負極活物質の製法の一例を以下で説明するが、これらに限定されるわけではない。 Although an example of the manufacturing method of the negative electrode active material containing the silicon oxycarbide and alkali metal salt of this invention is demonstrated below, it is not necessarily limited to these.
シリコンオキシカーバイドと、アルカリ金属及びアルカリ金属化合物からなる群より選ばれる少なくとも１種を含むアルカリ金属源と、を反応させて反応物を得て（工程１）、得られた反応物をアルコール、水及び酸性溶液からなる群より選ばれる少なくとも１種で洗浄処理する（工程２）ことで得ることができる。
＜工程１＞
本発明の製造方法において、＜工程１＞は説明すれば以下の通りである。シリコンオキシカーバイドとアルカリ金属及び／又はアルカリ金属化合物とを不活性ガス中で反応させて、シリコンオキシカーバイド中にアルカリ金属をドープさせた反応物を得る工程である。この反応時に、有機溶剤を用いることもできる。
A reaction product is obtained by reacting silicon oxycarbide with an alkali metal source containing at least one selected from the group consisting of alkali metals and alkali metal compounds (step 1). And at least one selected from the group consisting of acidic solutions (Step 2).
<Step 1>
In the production method of the present invention, <Step 1> will be described as follows. In this step, silicon oxycarbide is reacted with an alkali metal and / or an alkali metal compound in an inert gas to obtain a reaction product in which silicon oxycarbide is doped with an alkali metal. An organic solvent can also be used during this reaction.
シリコンオキシカーバイドとアルカリ金属を反応させる方法は特に限定されず、例えばシリコンオキシカーバイドとリチウムナフタレニドとをアルゴン雰囲気下、テトラヒドロフラン中で反応させる方法や、あるいはシリコンオキシカーバイドと金属リチウムをアルゴン雰囲気中でボールミル等の高せん断応力のかかる装置で混合し、反応させる方法により行うことができる。 The method of reacting silicon oxycarbide and alkali metal is not particularly limited. For example, silicon oxycarbide and lithium naphthalenide are reacted in tetrahydrofuran under argon atmosphere, or silicon oxycarbide and lithium metal are reacted in argon atmosphere. And can be carried out by a method of mixing and reacting in a device having high shear stress such as a ball mill.
シリコオキシカーバイドの形態は、特に限定されるものではないが、球状粒子、不定形粒子、繊維状等から適宜選択されるものであり、粉砕等の工程を経ることなく電極製造に用いることが可能な形態が好ましく、電極の厚み、密度（気孔率）あるいは目的とする蓄電デバイスの入出力特性、信頼性、安全性などを考慮して決定される。例えば、球状粒子、不定形粒子の場合の平均粒径、あるいは、繊維状材料の平均繊維長さは、好ましくは、通常５０μｍ以下であり、より好ましくは３０μｍ以下、更に好ましくは１０μｍ以下であり、下限は０．０１μｍ以上、好ましくは０．１μｍ以上、更に好ましくは０．５μｍ以上が実用的である。 The form of silicooxycarbide is not particularly limited, but is appropriately selected from spherical particles, amorphous particles, fibers, etc., and can be used for electrode production without undergoing a step such as grinding. This is preferably determined in consideration of the thickness and density (porosity) of the electrode or the input / output characteristics, reliability, safety, etc. of the target electricity storage device. For example, the average particle diameter in the case of spherical particles and irregular particles, or the average fiber length of the fibrous material is preferably usually 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less, The lower limit is 0.01 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more.
ここで用いるアルカリ金属源は、リチウム、ナトリウム、リチウム金属化合物、ナトリウム金属化合物などが挙げられる。リチウム金属化合物の例としては、リチウムナフタレニド、リチウムビフェニリド、水素化リチウム、ブチルリチウム、フェニルリチウムなどが挙げられる。ナトリウム金属化合物の例としては、ナトリウムナフタレニド、ナトリウムビフェニリド、水素化ナトリウムなどが挙げられる。これらは、単独で使用してもよく、２以上を適宜選択して使用してもよい。 Examples of the alkali metal source used here include lithium, sodium, a lithium metal compound, and a sodium metal compound. Examples of the lithium metal compound include lithium naphthalenide, lithium biphenylide, lithium hydride, butyl lithium, and phenyl lithium. Examples of sodium metal compounds include sodium naphthalenide, sodium biphenylide, sodium hydride and the like. These may be used alone, or two or more may be appropriately selected and used.
ここで使用する不活性ガスはアルゴン、窒素、ネオン、ヘリウム及びクリプトンからなる群より選ばれる１又は２以上の混合ガスであってもよい。 The inert gas used here may be one or two or more mixed gases selected from the group consisting of argon, nitrogen, neon, helium and krypton.
有機溶剤は、カーボネート類、ラクトン類、スルホン類、エーテル類、エステル類、炭化水素類から選ばれる１種又は２種以上の混合物であり、好ましくはカーボネート類、ラクトン類、スルホン類、エーテル類から選ばれる１種又は２種以上の混合物である。具体的には、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、メチルエチルカーボネート等のカーボネート類、テトラヒドロフラン、ジメトキシエタン、ジエチレングリコールジメチルエーテル、ジオキサン等のエーテル類、γ−ブチロラクトン等のラクトン類、スルホラン、ジプロピルスルホン等のスルホン類の１種又は２種以上からなる有機溶媒を用いることができる。ヘキサン、ドデカン、デカリン等の炭化水素、酢酸メチル、蟻酸メチル等のエステル類等も用いることが可能である。 The organic solvent is one or a mixture of two or more selected from carbonates, lactones, sulfones, ethers, esters and hydrocarbons, preferably from carbonates, lactones, sulfones and ethers. One kind or a mixture of two or more kinds selected. Specifically, carbonates such as propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and methyl ethyl carbonate, ethers such as tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and dioxane, lactones such as γ-butyrolactone, sulfolane, dioxane, and the like. An organic solvent composed of one or more sulfones such as propyl sulfone can be used. Hydrocarbons such as hexane, dodecane, and decalin, and esters such as methyl acetate and methyl formate can also be used.
シリコンオキシカーバイドへのアルカリ金属のドープ量は、アルカリ金属（ＭＡ）とシリコンオキシカーバイド中の珪素（Ｓｉ）との元素比（ＭＡ／Ｓｉ）で、０．１〜１０となる範囲が好ましく、２〜８の範囲であることがより好ましい。このような範囲とすることで、生産性が向上する。
＜工程２＞
本発明の製造方法において、「洗浄処理」とは、工程１で得られた反応物をアルカリ金属と反応する溶液で洗浄し、反応物中のアルカリ金属を失活させたアルカリ金属塩含有シリコンオキシカーバイドを得る工程である。反応物の洗浄に使用する溶液は、アルコール、水及び酸性溶液からなる群より選ばれる少なくとも１種のものを用いることができる。
The doping amount of alkali metal into silicon oxycarbide is preferably in the range of 0.1 to 10 in terms of element ratio (MA / Si) of alkali metal (MA) and silicon (Si) in silicon oxycarbide. More preferably, it is in the range of -8. Productivity improves by setting it as such a range.
<Process 2>
In the production method of the present invention, “cleaning treatment” means that the reaction product obtained in step 1 is washed with a solution that reacts with an alkali metal, and the alkali metal salt-containing silicon oxygen in which the alkali metal in the reaction product is deactivated. This is a step of obtaining carbide. The solution used for washing the reactant may be at least one selected from the group consisting of alcohol, water and acidic solution.
ここで用いるアルコールは、沸点が２００℃以下のアルコールを好適に用いることができる。アルコールの具体例として、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、１−ブタノール、２−ブタノール、ｔｅｒｔ−ブタノール、ｉｓｏ−ブタノール、エチレングリコールなどが挙げられる。 As the alcohol used here, an alcohol having a boiling point of 200 ° C. or lower can be suitably used. Specific examples of the alcohol include methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, tert-butanol, iso-butanol, ethylene glycol and the like.
ここで用いる酸性溶液は、無機酸、スルホン酸、カルボン酸などの溶液を好適に用いることができる。 As the acidic solution used here, a solution of inorganic acid, sulfonic acid, carboxylic acid or the like can be suitably used.
無機酸の具体例としては、塩酸、硝酸、硫酸、リン酸などが挙げられる。 Specific examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like.
カルボン酸の具体例としてはギ酸、酢酸、プロピオン酸、安息香酸、シュウ酸、クエン酸、酒石酸などが上げられる。スルホン酸の具体例としては、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸などが挙げられる
これらは、単独で使用してもよく、２以上を適宜選択して使用してもよい。
Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, benzoic acid, oxalic acid, citric acid, and tartaric acid. Specific examples of the sulfonic acid include methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid and the like. These may be used alone, or two or more may be appropriately selected and used. Also good.
具体的には、リチウムをドープしたシリコンオキシカーバイドに、不活性ガス中でエタノールを加え、ドープしたリチウムを失活させる。その後、反応物をろ過してエタノール、水で洗浄する。 Specifically, ethanol is added in an inert gas to lithium-doped silicon oxycarbide to deactivate the doped lithium. Thereafter, the reaction product is filtered and washed with ethanol and water.
洗浄方法は特に限定されず、例えば、反応物にエタノールを添加してそれをろ過し、ろ物をエタノール、１Ｎ塩酸の順に洗浄することで行うことができる。
＜工程２Ｂ＞
本発明の製造方法の別の態様として、前記工程１の後に、工程１で得られた反応物を酸素雰囲気又は窒素雰囲気中で加熱する工程を含めて行うことができる。工程１で得られた反応物中のリチウムは窒素および酸素と反応して失活させることができる。加熱温度は雰囲気により異なり、酸素雰囲気では２００℃〜５００℃の範囲が好ましく、２００℃〜３００℃がより好ましい。５００℃を超えるとシリコンオキシカーバイド中の炭素が分解するため好ましくない。窒素雰囲気では２００℃〜１０００℃の範囲が好ましく、３００℃〜７００℃がより好ましい。
The washing method is not particularly limited, and for example, ethanol can be added to the reaction product and filtered, and the filtrate can be washed in the order of ethanol and 1N hydrochloric acid.
<Process 2B>
As another aspect of the production method of the present invention, after the step 1, the reaction product obtained in the step 1 can be performed including a step of heating in an oxygen atmosphere or a nitrogen atmosphere. Lithium in the reaction product obtained in Step 1 can be deactivated by reacting with nitrogen and oxygen. The heating temperature varies depending on the atmosphere, and in an oxygen atmosphere, a range of 200 ° C to 500 ° C is preferable, and 200 ° C to 300 ° C is more preferable. If it exceeds 500 ° C., carbon in silicon oxycarbide is decomposed, which is not preferable. In a nitrogen atmosphere, the range of 200 ° C to 1000 ° C is preferable, and 300 ° C to 700 ° C is more preferable.
加熱する方法は特に限定されないが、加熱機構を有する反応装置を用いればよく、連続法、回分法での処理が可能で、具体的には流動層反応炉、回転炉、竪型移動層反応炉、トンネル炉、バッチ炉、ロータリーキルン等をその目的に応じ適宜選択することができる。 The heating method is not particularly limited, but a reactor having a heating mechanism may be used, and processing by a continuous method or a batch method is possible. Specifically, a fluidized bed reactor, a rotary furnace, a vertical moving bed reactor A tunnel furnace, a batch furnace, a rotary kiln and the like can be appropriately selected according to the purpose.
上述の製法で得られた本発明の負極活物質は、シリコンオキシカーバイド中のアルカリ金属および／又はアルカリ金属化合物は失活し、アルカリ金属塩となって存在している。
＜非水電解質二次電池の作製＞
非水電解質二次電池負極は、本発明の非水電解質二次電池負極活物質とバインダーとを必須成分として、必要に応じてその他の導電助剤などの成分を含んで構成される。こうして得られる負極は、活物質として、本発明の非水電解質二次電池負極活物質を含むことから、大気中での取扱いも容易で、高容量かつ優れたサイクル特性を有し、さらに、優れた初回クーロン効率をも兼備する非水電解質二次電池用負極となる。該負極は、例えば、前述の非水電解質二次電池用負極活物質と、有機結着材であるバインダーとを、溶剤とともに撹拌機、ボールミル、スーパーサンドミル、加圧ニーダ等の分散装置により混練して、負極材スラリーを調製し、これを集電体に塗布して負極層を形成することで得ることができる。また、ペースト状の負極材スラリーをシート状、ペレット状等の形状に成形し、これを集電体と一体化することでも得ることができる。
In the negative electrode active material of the present invention obtained by the above-described production method, the alkali metal and / or alkali metal compound in silicon oxycarbide is deactivated and exists as an alkali metal salt.
<Preparation of nonaqueous electrolyte secondary battery>
The non-aqueous electrolyte secondary battery negative electrode includes the non-aqueous electrolyte secondary battery negative electrode active material of the present invention and a binder as essential components, and includes other components such as a conductive additive as necessary. Since the negative electrode thus obtained contains the non-aqueous electrolyte secondary battery negative electrode active material of the present invention as an active material, it is easy to handle in the atmosphere, has a high capacity and excellent cycle characteristics, In addition, it becomes a negative electrode for a non-aqueous electrolyte secondary battery that also has the first-time coulomb efficiency. The negative electrode is prepared by, for example, kneading the negative electrode active material for a non-aqueous electrolyte secondary battery and a binder, which is an organic binder, with a dispersion apparatus such as a stirrer, a ball mill, a super sand mill, and a pressure kneader. Thus, a negative electrode material slurry is prepared and applied to a current collector to form a negative electrode layer. Alternatively, the paste-like negative electrode material slurry can be formed into a sheet shape, a pellet shape or the like and integrated with the current collector.
上記有機結着剤（本願明細書において「バインダー」ともいう）としては、特に限定されないが、例えば、スチレン−ブタジエン共重合体；エチレン性不飽和カルボン酸エステル（例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、（メタ）アクリロニトリル、およびヒドロキシエチル（メタ）アクリレート等）、およびエチレン性不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等）からなる（メタ）アクリル共重合体；ポリ弗化ビニリデン、ポリエチレンオキサイド、ポリエピクロヒドリン、ポリホスファゼン、ポリアクリロニトリル、ポリイミド、ポリアミドイミド、カルボキシメチルセルロースなどの高分子化合物が挙げられる。 The organic binder (also referred to as “binder” in the present specification) is not particularly limited. For example, styrene-butadiene copolymer; ethylenically unsaturated carboxylic acid ester (for example, methyl (meth) acrylate, ethyl (Meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, and hydroxyethyl (meth) acrylate), and ethylenically unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid) And (meth) acrylic copolymers; polymer compounds such as polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polyimide, polyamideimide, and carboxymethylcellulose.
これらの有機結着剤は、それぞれの物性によって、水に分散、あるいは溶解したもの、また、Ｎ‐メチル‐２‐ピロリドン（ＮＭＰ）などの有機溶剤に溶解したものがある。リチウムイオン二次電池負極の負極層中の有機結着剤の含有比率は、１〜３０質量％であることが好ましく、２〜２０質量％であることがより好ましく、３〜１５質量％であることがさらに好ましい。 These organic binders may be dispersed or dissolved in water or dissolved in an organic solvent such as N-methyl-2-pyrrolidone (NMP) depending on the respective physical properties. The content ratio of the organic binder in the negative electrode layer of the lithium ion secondary battery negative electrode is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 15% by mass. More preferably.
有機結着剤の含有比率が１質量％以上であることで密着性が良好で、充放電時の膨張・収縮によって負極が破壊されることが抑制される。一方、３０質量％以下であることで、電極抵抗が大きくなることを抑制できる。 Adhesion is good when the content ratio of the organic binder is 1% by mass or more, and destruction of the negative electrode due to expansion / contraction during charge / discharge is suppressed. On the other hand, it can suppress that electrode resistance becomes large because it is 30 mass% or less.
この際、本発明においては、水性バインダーも採用することができる点で、実用化面においても従来のリチウムドープ技術に比べて優れるものである。 In this case, the present invention is superior to the conventional lithium doping technique in terms of practical use in that an aqueous binder can also be used.
また、上記負極材スラリーには、必要に応じて、導電助材を混合してもよい。導電助材としては、例えば、カーボンブラック、グラファイト、アセチレンブラック、あるいは導電性を示す酸化物や窒化物等が挙げられる。導電助剤の使用量は、本発明のリチウムイオン二次電池負極材に対して１〜１５質量％程度とすればよい。 Moreover, you may mix a conductive support material with the said negative electrode material slurry as needed. Examples of the conductive aid include carbon black, graphite, acetylene black, or conductive oxides and nitrides. The usage-amount of a conductive support agent should just be about 1-15 mass% with respect to the lithium ion secondary battery negative electrode material of this invention.
また前記集電体の材質および形状については、特に限定されず、例えば、アルミニウム、銅、ニッケル、チタン、ステンレス鋼等を、箔状、穴開け箔状、メッシュ状等にした帯状のものを用いればよい。また、多孔性材料、たとえばポーラスメタル（発泡メタル）やカーボンペーパーなども使用可能である。 Further, the material and shape of the current collector are not particularly limited, and for example, a strip-shaped material made of aluminum, copper, nickel, titanium, stainless steel or the like in a foil shape, a punched foil shape, a mesh shape, or the like is used. That's fine. A porous material such as porous metal (foamed metal) or carbon paper can also be used.
上記負極材スラリーを集電体に塗布する方法としては、特に限定されないが、例えば、メタルマスク印刷法、静電塗装法、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法など公知の方法が挙げられる。塗布後は、必要に応じて平板プレス、カレンダーロール等による圧延処理を行うことが好ましい。 The method of applying the negative electrode material slurry to the current collector is not particularly limited. For example, metal mask printing method, electrostatic coating method, dip coating method, spray coating method, roll coating method, doctor blade method, gravure coating And publicly known methods such as screen printing and the like. After the application, it is preferable to perform a rolling process using a flat plate press, a calender roll or the like, if necessary.
また、シート状、ペレット状等の形状に成形された負極材スラリーと集電体との一体化は、例えば、ロール、プレス、もしくはこれらの組み合わせ等、公知の方法により行うことができる。 Further, the integration of the negative electrode material slurry formed into a sheet shape, a pellet shape, and the like with the current collector can be performed by a known method such as a roll, a press, or a combination thereof.
前記集電体上に形成された負極層および集電体と一体化した負極層は、用いた有機結着剤に応じて熱処理することが好ましい。例えば、ポリイミド、ポリアミドイミドを主骨格とした有機結着剤を用いた場合には１５０〜４５０℃で熱処理することが好ましい。 The negative electrode layer formed on the current collector and the negative electrode layer integrated with the current collector are preferably heat-treated according to the organic binder used. For example, when an organic binder having a main skeleton of polyimide or polyamideimide is used, heat treatment is preferably performed at 150 to 450 ° C.
この熱処理により溶媒の除去、バインダーの硬化による高強度化が進み、粒子間及び粒子と集電体間の密着性が向上できる。尚、これらの熱処理は、処理中の集電体の酸化を防ぐため、ヘリウム、アルゴン、窒素等の不活性雰囲気、真空雰囲気で行うことが好ましい。 This heat treatment increases the strength by removing the solvent and curing the binder, thereby improving the adhesion between the particles and between the particles and the current collector. These heat treatments are preferably performed in an inert atmosphere such as helium, argon, nitrogen, or a vacuum atmosphere in order to prevent oxidation of the current collector during the treatment.
また、熱処理する前に、負極はプレス（加圧処理）しておくことが好ましい。本発明の非水電解質二次電池用負極材では、電極密度が１．１〜１．７ｇ／ｃｍ３であることが好ましく、１．２〜１．７ｇ／ｃｍ３であることがより好ましく、１．３〜１．７ｇ／ｃｍ３であることがさらに好ましい。電極密度については、高いほど密着性が向上し、サイクル性も向上する傾向がある。 In addition, the negative electrode is preferably pressed (pressurized) before the heat treatment. The negative electrode material for non-aqueous electrolyte secondary battery of the present invention, it is preferable that the electrode density of 1.1~1.7g / cm 3, more preferably 1.2~1.7g / cm 3, More preferably, it is 1.3-1.7 g / cm 3 . About electrode density, it exists in the tendency for adhesiveness to improve and cycling property, so that it is high.
本発明の非水電解質二次電池は、既述の本発明の負極を用いてなることを特徴とする。例えば、正極と、本発明の負極とを、セパレータを介して対向して配置し、電解液を注入することにより構成することができる。 The nonaqueous electrolyte secondary battery of the present invention is characterized by using the above-described negative electrode of the present invention. For example, the positive electrode and the negative electrode of the present invention can be arranged so as to face each other with a separator interposed therebetween and injected with an electrolytic solution.
前記正極は、前記負極と同様にして、集電体表面上に正極層を形成することで得ることができる。この場合の集電体はアルミニウム、チタン、ステンレス鋼等の金属や合金を、箔状、穴開け箔状、メッシュ状等にした帯状のものを用いることができる。 The positive electrode can be obtained by forming a positive electrode layer on the current collector surface in the same manner as the negative electrode. In this case, the current collector may be a band-shaped material made of a metal or an alloy such as aluminum, titanium, or stainless steel in a foil shape, a punched foil shape, a mesh shape, or the like.
前記正極層に用いる正極材料としては、特に制限されない。非水電解質二次電池の中でも、リチウムイオン二次電池を作製する場合には、例えば、リチウムイオンをドーピングまたはインターカレーション可能な金属化合物、金属酸化物、金属硫化物、または導電性高分子材料を用いればよく、特に限定されない。例えば、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）、およびこれらの複酸化物（ＬｉＣｏｘＮｉｙＭｎｚＯ２、ｘ＋ｙ＋ｚ＝１）、リチウムマンガンスピネル（ＬｉＭｎ２Ｏ４）、リチウムバナジウム化合物、Ｖ２Ｏ５、Ｖ６Ｏ１３、ＶＯ２、ＭｎＯ２、ＴｉＯ２、ＭｏＶ２Ｏ８、ＴｉＳ２、Ｖ２Ｓ５、ＶＳ２、ＭｏＳ２、ＭｏＳ３、Ｃｒ３Ｏ８、Ｃｒ２Ｏ５、オリビン型ＬｉＭＰＯ４（Ｍ：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ）、ポリアセチレン、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセン等の導電性ポリマー、多孔質炭素等などを単独或いは混合して使用することができる。 The positive electrode material used for the positive electrode layer is not particularly limited. When producing a lithium ion secondary battery among nonaqueous electrolyte secondary batteries, for example, a metal compound, metal oxide, metal sulfide, or conductive polymer material capable of doping or intercalating lithium ions There is no particular limitation. For example, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), and their double oxides (LiCoxNiyMnzO 2 , x + y + z = 1), lithium manganese spinel (LiMn 2 O 4 ) , Lithium vanadium compound, V 2 O 5 , V 6 O 13 , VO 2 , MnO 2 , TiO 2 , MoV 2 O 8 , TiS 2 , V 2 S 5 , VS 2 , MoS 2 , MoS 3 , Cr 3 O 8 , Cr 2 O 5 , olivine-type LiMPO 4 (M: Co, Ni, Mn, Fe), polyacetylene, polyaniline, polypyrrole, polythiophene, polyacene and other conductive polymers, porous carbon, etc. are used alone or in combination. be able to.
前記セパレータとしては、例えば、ポリエチレン、ポリプロピレン等のポリオレフィンを主成分とした不織布、クロス、微孔フィルム又はそれらを組み合わせたものを使用することができる。なお、作製する非水電解質二次電池の正極と負極が直接接触しない構造にした場合は、セパレータを使用する必要はない。 As the separator, for example, a nonwoven fabric mainly composed of polyolefin such as polyethylene and polypropylene, cloth, microporous film, or a combination thereof can be used. In addition, when it is set as the structure where the positive electrode and negative electrode of the nonaqueous electrolyte secondary battery to produce are not in direct contact, it is not necessary to use a separator.
前記電解液としては、例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＡｓＦ６、ＬｉＢＦ４、ＬｉＳＯ３ＣＦ３等のリチウム塩を、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ビニレンカーボネート、フルオロエチレンカーボネート、シクロペンタノン、スルホラン、３−メチルスルホラン、２，４−ジメチルスルホラン、３−メチル−１，３−オキサゾリジン−２−オン、γ−ブチロラクトン、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、ブチルメチルカーボネート、エチルプロピルカーボネート、ブチルエチルカーボネート、ジプロピルカーボネート、１，２−ジメトキシエタン、テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、酢酸メチル、酢酸エチル等の単体もしくは２成分以上の混合物の非水系溶剤に溶解した、いわゆる有機電解液を使用することができる。 Examples of the electrolyte include lithium salts such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, cyclopentanone, Sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, 3-methyl-1,3-oxazolidine-2-one, γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, Ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1 , 3-dioxolane, methyl acetate, ethyl acetate or the like, or a so-called organic electrolyte solution dissolved in a non-aqueous solvent of a mixture of two or more components can be used.
本発明の非水電解質二次電池の構造は、特に限定されないが、通常、正極および負極と、必要に応じて設けられるセパレータとを、扁平渦巻状に巻回して巻回式極板群としたり、これらを平板状として積層して積層式極板群としたりし、これら極板群を外装体中に封入した構造とするのが一般的である。 The structure of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited. Usually, a positive electrode and a negative electrode, and a separator provided as necessary, are wound into a flat spiral shape to form a wound electrode group. In general, these are laminated as a flat plate to form a laminated electrode plate group, and the electrode plate group is sealed in an exterior body.
本発明の非水電解質二次電池は、特に限定されないが、ペーパー型電池、ボタン型電池、コイン型電池、積層型電池、円筒型電池、角型電池などとして使用される。 Although the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, it is used as a paper-type battery, a button-type battery, a coin-type battery, a laminated battery, a cylindrical battery, a rectangular battery, or the like.
上述した本発明のシリコンオキシカーバイドは、リチウムイオンを挿入脱離することを充放電機構とする電気化学装置全般、例えば、ハイブリッドキャパシタなどにも適用することが可能である。 The above-described silicon oxycarbide of the present invention can be applied to all electrochemical devices having a charge / discharge mechanism that inserts and desorbs lithium ions, for example, a hybrid capacitor.
次に、本発明を、実施例及び比較例により具体的に説明する。特に断りがない限り「部」「％」は質量基準である。 Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise specified, “part” and “%” are based on mass.
まず、本発明の目的物の評価・確認手段を以下に示す。
＜元素分析＞
本発明の各元素の含有量は以下の分析により評価した。
Ｃ分析：高周波燃焼−赤外線吸収法により、分析を行った。
装置：ＬＥＣＯ製 ＣＳ ８４４ 型
Ｏ分析：不活性ガス融解−赤外線吸収法により、分析を行った。
装置：ＬＥＣＯ製 ＴＣＨ６００型
Ｓｉ、Ｌi分析：試料を水酸化ナトリウムと過酸化ナトリウムで溶解分解後、溶融物を塩酸で溶解した後、ＩＣＰ検出を行った。
装置：島津製作所製 ＩＣＰＥ−９８２０ 型
＜本発明の負極活物質において、リチウムが失活している（リチウム塩として存在している）ことの確認手段＞
シリコンオキシカーバイド中のリチウムの失活は、リチウム塩含有シリコンオキシカーバイドに水を加えて、水素が発生しないことからリチウムの失活を確認した。
First, evaluation / confirmation means for the object of the present invention will be described below.
<Elemental analysis>
The content of each element of the present invention was evaluated by the following analysis.
C analysis: Analysis was performed by a high-frequency combustion-infrared absorption method.
Apparatus: manufactured by LECO, CS 844 type O analysis: Analysis was performed by inert gas melting-infrared absorption method.
Apparatus: LECO TCH600 type Si, Li analysis: The sample was dissolved and decomposed with sodium hydroxide and sodium peroxide, and the melt was dissolved with hydrochloric acid, followed by ICP detection.
Device: ICPE-9820 model manufactured by Shimadzu Corporation <Means for confirming that lithium is deactivated (present as lithium salt) in the negative electrode active material of the present invention>
The deactivation of lithium in silicon oxycarbide was confirmed by adding water to the lithium salt-containing silicon oxycarbide to prevent generation of hydrogen.
水素の発生の有無は以下の方法で確認した。シュレンク管にリチウム含有シリコンオキシカーバイドを１g加えて、管内をアルゴン雰囲気に置換し、その後、水１０ｍｌを加えて１時間攪拌した。攪拌後のシュレンク管からロック型シリンジを使用してガスを採取し、ガスクロマトグラフ（島津製作所製 ＧＣ−２０１４ 型）を用いて採取したガスを分析し、水素発生の有無を確認した。 The presence or absence of hydrogen generation was confirmed by the following method. 1 g of lithium-containing silicon oxycarbide was added to the Schlenk tube, the inside of the tube was replaced with an argon atmosphere, and then 10 ml of water was added and stirred for 1 hour. Gas was collected from the Schlenk tube after stirring using a lock syringe, and the collected gas was analyzed using a gas chromatograph (GC-2014 model, manufactured by Shimadzu Corporation) to confirm the presence or absence of hydrogen generation.
＜電池特性の評価＞
本発明のリチウム塩含有シリコンオキシカーバイド粒子の電池特性を次のようにして測定した。
測定の際に設定した電流値は、リチウム塩含有シリコンオキシカーバイド粒子あたりの理論容量を７００ｍＡｈ（１．０Ｃ）とし、リチウム塩含有シリコンオキシカーバイド粒子重量あたり７０ｍＡ（０．１Ｃ）となるようにした。
<Evaluation of battery characteristics>
The battery characteristics of the lithium salt-containing silicon oxycarbide particles of the present invention were measured as follows.
The current value set at the time of measurement was such that the theoretical capacity per lithium salt-containing silicon oxycarbide particles was 700 mAh (1.0 C), and 70 mA (0.1 C) per lithium salt-containing silicon oxycarbide particle weight. .
二次電池充放電試験装置（北斗電工）を用いて電池特性を測定し、充電は電池電圧が０．００５Ｖに達するまで０．１Ｃの電流値でおこない、０．００５Ｖに達した後は、セル電圧を０．００５Ｖに保つように電流を減少させて行った。そして、電流値が１０分の１の電流値を下回った時点で充電を終了した。このときの容量を充電容量とした。放電は０．１Ｃの電流値で行い、電圧が１．５Ｖを上回った時点で終了した。このときの容量を放電容量とした。各充放電時の切り替え時には、３０分間、開回路で放置した。クーロン効率は以下のようにして求めた。
クーロン効率（％） ＝ 放電容量（ｍＡｈ／ｇ） ／ 充電容量（ｍＡｈ／ｇ）
Battery characteristics were measured using a secondary battery charge / discharge test device (Hokuto Denko). Charging was performed at a current value of 0.1 C until the battery voltage reached 0.005 V, and after reaching 0.005 V, the cell The current was decreased so as to keep the voltage at 0.005V. And charging was complete | finished when the electric current value fell below the electric current value of 1/10. The capacity at this time was defined as a charging capacity. Discharging was performed at a current value of 0.1 C, and ended when the voltage exceeded 1.5V. The capacity at this time was defined as a discharge capacity. At the time of switching at each charge / discharge, it was left in an open circuit for 30 minutes. Coulomb efficiency was obtained as follows.
Coulomb efficiency (%) = discharge capacity (mAh / g) / charge capacity (mAh / g)
＜珪素含有複合樹脂（Ａ）の合成＞
［合成例１］
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、フェニルトリメトキシシラン（ＰＴＭＳ）１６４ｇを仕込んで、１２０℃まで昇温した。次いで、メチルメタクリレート（ＭＭＡ）２２６ｇ、３−メタクリロイルオキシプロピルトリメトキシシラン（ＭＰＴＳ）１４ｇ、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート２４ｇからなる混合物を、前記反応容器中へ４時間で滴下した。その後、同温度で１６時間撹拌し、トリメトキシシリル基を有するビニル重合体を調製した。
<Synthesis of silicon-containing composite resin (A)>
[Synthesis Example 1]
Into a reaction vessel equipped with a stirrer, thermometer, dropping funnel, condenser and nitrogen gas inlet, 164 g of phenyltrimethoxysilane (PTMS) was charged and heated to 120 ° C. Subsequently, a mixture consisting of 226 g of methyl methacrylate (MMA), 14 g of 3-methacryloyloxypropyltrimethoxysilane (MPTS), and 24 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction vessel over 4 hours. . Thereafter, the mixture was stirred at the same temperature for 16 hours to prepare a vinyl polymer having a trimethoxysilyl group.
次いで、前記反応容器の温度を８０℃に調整し、メチルトリメトキシシラン（ＭＴＭＳ）１１３ｇ、３−アクリロイルオキシプロピルトリメトキシシラン（ＡＰＴＳ）１９４ｇ、ジメチルジメトキシシラン（ＤＭＤＭＳ）９９ｇを、前記反応容器中へ添加した。 その後、Ｐｈｏｓｌｅｘ Ａ−３〔堺化学（株）製、イソプロピルアシッドホスフェイト〕５．４ｇと脱イオン水 ８３ｇとの混合物を、５分間で滴下し、同温度で２時間撹拌することにより、加水分解縮合反応させ、反応生成物を得た。反応生成物を、１Ｈ−ＮＭＲを用いて分析したところ、前記ビニル重合体が有するトリメトキシシリル基のほぼ１００％が加水分解していた。その後、前記反応生成物を、１０〜３００ｍｍＨｇの減圧下に、４０〜６０℃の条件で２時間蒸留することにより、生成したメタノール及び水を除去し、次いで、酢酸ブチル（ＢｕＡｃ） ４００ｇを添加することで、不揮発分が５９．８質量％であるポリシロキサンセグメントとビニル重合体セグメントからなる珪素含有複合樹脂（Ａ−１）の溶液 １０００ｇを得た。 Next, the temperature of the reaction vessel was adjusted to 80 ° C., and 113 g of methyltrimethoxysilane (MTMS), 194 g of 3-acryloyloxypropyltrimethoxysilane (APTS), and 99 g of dimethyldimethoxysilane (DMDMS) were introduced into the reaction vessel. Added. Thereafter, a mixture of 5.4 g of Phoslex A-3 [manufactured by Sakai Chemical Co., Ltd., isopropyl acid phosphate] and 83 g of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours for hydrolysis. A condensation reaction was performed to obtain a reaction product. When the reaction product was analyzed using 1H-NMR, almost 100% of the trimethoxysilyl group of the vinyl polymer was hydrolyzed. Thereafter, the reaction product is distilled under reduced pressure of 10 to 300 mmHg at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 400 g of butyl acetate (BuAc) is added. Thus, 1000 g of a silicon-containing composite resin (A-1) solution composed of a polysiloxane segment having a nonvolatile content of 59.8% by mass and a vinyl polymer segment was obtained.
［合成例２］
前記合成例１と同様の反応容器に、ＰＴＭＳ １９１ｇを仕込んで、１２０℃まで昇温した。次いで、ＭＭＡ １６９ｇ、ＭＰＴＳ １１ｇ、ＴＢＰＥＨ １８ｇからなる混合物を、前記反応容器中へ４時間で滴下した。その後、同温度で１６時間撹拌することにより、トリメトキシシリル基を有するビニル重合体を調製した。
[Synthesis Example 2]
In the same reaction vessel as in Synthesis Example 1, 191 g of PTMS was charged and the temperature was raised to 120 ° C. Subsequently, a mixture consisting of 169 g of MMA, 11 g of MPTS, and 18 g of TBPEH was dropped into the reaction vessel over 4 hours. Then, the vinyl polymer which has a trimethoxysilyl group was prepared by stirring at the same temperature for 16 hours.
次いで、前記反応容器の温度を８０℃に調整し、ＭＴＭＳ ４５４ｇ、ＤＭＤＭＳ １１６ｇを添加した。その後、Ｐｈｏｓｌｅｘ Ａ−３ ８．４ｇと脱イオン水 １３４ｇとの混合物を、５分間で滴下し、同温度で２時間撹拌することにより、加水分解縮合反応させ、反応生成物を得た。反応生成物を、１Ｈ−ＮＭＲを用いて分析したところ、前記ビニル重合体が有するトリメトキシシリル基のほぼ１００％が加水分解していた。その後、前記反応生成物を、１０〜３００ｍｍＨｇの減圧下に、４０〜６０℃の条件で２時間蒸留することにより、生成したメタノール及び水を除去し、次いで、ＢｕＡｃ ４００ｇを添加することで、不揮発分が６０．１％である重合性二重結合を有さないポリシロキサンセグメントとビニル重合体セグメントからなる珪素含有複合樹脂（Ａ−２）の溶液 １０００ｇを得た。 Subsequently, the temperature of the reaction vessel was adjusted to 80 ° C., and 454 g of MTMS and 116 g of DMDMS were added. Thereafter, a mixture of 8.4 g of Phoslex A-3 and 134 g of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours to cause a hydrolysis and condensation reaction, thereby obtaining a reaction product. When the reaction product was analyzed using 1H-NMR, almost 100% of the trimethoxysilyl group of the vinyl polymer was hydrolyzed. Thereafter, the reaction product is distilled under a reduced pressure of 10 to 300 mmHg for 2 hours under the conditions of 40 to 60 ° C. to remove the generated methanol and water, and then 400 g of BuAc is added to be non-volatile. 1000 g of a solution of a silicon-containing composite resin (A-2) comprising a polysiloxane segment having no polymerizable double bond and a vinyl polymer segment with a content of 60.1% was obtained.
［実施例１］
合成例１で得られた珪素含有複合樹脂（Ａ−１）の溶液２００ｇを、減圧下１００℃で１２時間乾燥させた。乾燥物を１０００℃３時間窒素雰囲気中で加熱し、黒色のシリコンオキシカーバイド固形物を得た。得られた固形物をペイントコンディショナーで粉砕し、平均粒径１０μｍのシリコンオキシカーバイド粒子を得た。シリコンオキシカーバイド粒子の組成式は、ＳｉＯｙＣｚと表した場合に、（Ｓｉが１．００、Ｏ（ｙ）が１．５３、Ｃ（ｚ）が１．５４）であった。
得られたシリコンオキシカーバイド粒子 １．５ｇ、リチウム ０．５８ｇ、ナフタレン １１ｇ、テトラヒドロフラン（ＴＨＦ）５０ｍｌをアルゴン中で混合し、３時間攪拌した。その後、得られた反応液にイソプロパノール２０ｍｌを徐々に加えて、次いで水２０ｍｌを徐々に加えた。反応液をろ過し、黒色のろ物を水、塩酸で洗浄した。洗浄したろ物を減圧下で１２時間乾燥し、リチウム塩含有シリコンオキシカーバイド粒子を得た。得られたリチウム塩含有シリコンオキシカーバイド粒子１ｇに水１０ｍｌを添加して攪拌したところ、水素の発生は確認できなかった。リチウム塩含有シリコンオキシカーバイド粒子に含まれるリチウム塩の量（Ｌｉ／Ｓｉの値）は０．６４であった。
[Example 1]
200 g of the silicon-containing composite resin (A-1) solution obtained in Synthesis Example 1 was dried at 100 ° C. under reduced pressure for 12 hours. The dried product was heated at 1000 ° C. for 3 hours in a nitrogen atmosphere to obtain a black silicon oxycarbide solid. The obtained solid was pulverized with a paint conditioner to obtain silicon oxycarbide particles having an average particle size of 10 μm. The composition formula of the silicon oxycarbide particles was (Si is 1.00, O (y) is 1.53, and C (z) is 1.54) when expressed as SiOyCz.
The obtained silicon oxycarbide particles 1.5 g, lithium 0.58 g, naphthalene 11 g and tetrahydrofuran (THF) 50 ml were mixed in argon and stirred for 3 hours. Thereafter, 20 ml of isopropanol was gradually added to the resulting reaction solution, and then 20 ml of water was gradually added. The reaction solution was filtered, and the black residue was washed with water and hydrochloric acid. The washed filtrate was dried under reduced pressure for 12 hours to obtain lithium salt-containing silicon oxycarbide particles. When 10 ml of water was added to 1 g of the obtained lithium salt-containing silicon oxycarbide particles and stirred, generation of hydrogen could not be confirmed. The amount of lithium salt (value of Li / Si) contained in the lithium salt-containing silicon oxycarbide particles was 0.64.
［実施例２］
合成例２で得られた珪素含有複合樹脂（Ａ−２）の溶液２００ｇを、減圧下１００℃で１２時間乾燥させた。乾燥物を１０００℃３時間窒素雰囲気中で加熱し、黒色のシリコンオキシカーバイド固形物を得た。得られた固形物をペイントコンディショナーで粉砕し、平均粒径１０μｍのシリコンオキシカーバイド粒子を得た。シリコンオキシカーバイド粒子の組成式は、ＳｉＯｙＣｚと表した場合に、（Ｓｉが１．００、Ｏ（ｙ）が１．４７、Ｃ（ｚ）が１．４７）であった。
得られたシリコンオキシカーバイド粒子 １．５ｇ、リチウム ０．５８ｇ、ナフタレン １１ｇ、テトラヒドロフラン（ＴＨＦ）５０ｍｌをアルゴン中で混合し、３時間攪拌した。その後、得られた反応液にイソプロパノール２０ｍｌを徐々に加えて、次いで水２０ｍｌを徐々に加えた。反応液をろ過し、黒色のろ物を水、塩酸で洗浄した。洗浄したろ物を減圧下で１２時間乾燥し、リチウム塩含有シリコンオキシカーバイド粒子を得た。得られたリチウム塩含有シリコンオキシカーバイド粒子１ｇに水１０ｍｌを添加して攪拌したところ、水素の発生は確認できなかった。リチウム塩含有シリコンオキシカーバイド粒子に含まれるリチウム塩の量（Ｌｉ／Ｓｉの値）は０．５８であった。
[Example 2]
200 g of the silicon-containing composite resin (A-2) solution obtained in Synthesis Example 2 was dried at 100 ° C. under reduced pressure for 12 hours. The dried product was heated at 1000 ° C. for 3 hours in a nitrogen atmosphere to obtain a black silicon oxycarbide solid. The obtained solid was pulverized with a paint conditioner to obtain silicon oxycarbide particles having an average particle size of 10 μm. The composition formula of the silicon oxycarbide particles was (Si is 1.00, O (y) is 1.47, and C (z) is 1.47) when expressed as SiOyCz.
The obtained silicon oxycarbide particles 1.5 g, lithium 0.58 g, naphthalene 11 g and tetrahydrofuran (THF) 50 ml were mixed in argon and stirred for 3 hours. Thereafter, 20 ml of isopropanol was gradually added to the resulting reaction solution, and then 20 ml of water was gradually added. The reaction solution was filtered, and the black residue was washed with water and hydrochloric acid. The washed filtrate was dried under reduced pressure for 12 hours to obtain lithium salt-containing silicon oxycarbide particles. When 10 ml of water was added to 1 g of the obtained lithium salt-containing silicon oxycarbide particles and stirred, generation of hydrogen could not be confirmed. The amount of lithium salt (Li / Si value) contained in the lithium salt-containing silicon oxycarbide particles was 0.58.
［試験例１］
実施例１で得られたリチウム塩含有シリコンオキシカーバイド粒子 ８０部に対して、アセチレンブラック１０部、カルボキシメチルセルロースナトリウム２．５部、スチレンブタジエンゴム７．５部、水１５０部を加えてスラリーを作製した。次いで、スラリーを厚さ１８μｍの銅箔に塗布し、１２０℃で１時間乾燥後、プレスにより電極を加圧成形し、最終的には１．５４ｃｍ２に打ち抜き、負極とした。得られた負極と対極にリチウム箔を使用し、非水電解質として六フッ化リンリチウムをエチレンカーボネートとジエチルカーボネートの１／１（体積比）混合液に１ｍｏｌ／Ｌの濃度で溶解した非水電解質溶液を用い、セパレータに厚さ３０μｍのポリエチレン製微多孔質フィルムを用いた評価用リチウムイオン二次電池ハーフセルを作製した。
[Test Example 1]
A slurry was prepared by adding 10 parts of acetylene black, 2.5 parts of sodium carboxymethylcellulose, 7.5 parts of styrene butadiene rubber, and 150 parts of water to 80 parts of the lithium salt-containing silicon oxycarbide particles obtained in Example 1. did. Next, the slurry was applied to a copper foil having a thickness of 18 μm, dried at 120 ° C. for 1 hour, and then the electrode was press-molded by a press, and finally punched to 1.54 cm 2 to form a negative electrode. A non-aqueous electrolyte in which lithium foil is used for the obtained negative electrode and counter electrode, and lithium hexafluoride is dissolved as a non-aqueous electrolyte in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / L. Using the solution, a lithium ion secondary battery half cell for evaluation using a polyethylene microporous film having a thickness of 30 μm as a separator was produced.
得られたハーフセルを１２時間室温で放置した後、二次電池充放電試験装置（北斗電工）を用いて、初回の充放電容量および初回クーロン効率を評価した。結果を表３に示す。 After the obtained half cell was allowed to stand at room temperature for 12 hours, the initial charge / discharge capacity and the initial coulomb efficiency were evaluated using a secondary battery charge / discharge test apparatus (Hokuto Denko). The results are shown in Table 3.
［試験例２］
実施例２で得られたリチウム塩含有シリコンオキシカーバイド粒子を用いたこと以外は、前記試験例１と同様にして、電池を作製し、電池特性を評価した。結果を表３に示す。
[Test Example 2]
A battery was prepared and the battery characteristics were evaluated in the same manner as in Test Example 1 except that the lithium salt-containing silicon oxycarbide particles obtained in Example 2 were used. The results are shown in Table 3.
＜比較例＞
［比較実施例］
合成例１で得られた珪素含有複合樹脂の溶液２００ｇを、減圧下１００℃で１２時間乾燥させた。乾燥物を１０００℃３時間窒素雰囲気中で加熱し、黒色のシリコンオキシカーバイド固形物を得た。得られた固形物をペイントコンディショナーで粉砕し、平均粒径１０μｍのシリコンオキシカーバイド粒子を得た。得られたシリコンオキシカーバイド粒子 １．５ｇに対して、アルゴン雰囲気中でリチウム粉を０．１ｇ添加して乳鉢で攪拌混合し、リチウムドープしたシリコンオキシカーバイド粒子を得た。得られたリチウムドープされたシリコンオキシカーバイド粒子１ｇに水１０ｍｌを添加したところ、水素の発生が確認された。
<Comparative example>
[Comparative Example]
200 g of the silicon-containing composite resin solution obtained in Synthesis Example 1 was dried at 100 ° C. under reduced pressure for 12 hours. The dried product was heated at 1000 ° C. for 3 hours in a nitrogen atmosphere to obtain a black silicon oxycarbide solid. The obtained solid was pulverized with a paint conditioner to obtain silicon oxycarbide particles having an average particle size of 10 μm. To 1.5 g of the obtained silicon oxycarbide particles, 0.1 g of lithium powder was added in an argon atmosphere and mixed with stirring in a mortar to obtain lithium-doped silicon oxycarbide particles. When 10 ml of water was added to 1 g of the obtained lithium-doped silicon oxycarbide particles, generation of hydrogen was confirmed.
［比較試験例１］
比較実施例で得られたリチウム含有シリコンオキシカーバイド粒子８０部に対して、アセチレンブラック１０部、ポリ弗化ビニリデン１０部、ＮＭＰ１５０部を加えてスラリーを作製した。次いで、スラリーを厚さ１８μｍの銅箔に塗布し、リチウム含有シリコンオキシカーバイドを含む負極を作製し、得られたリチウム含有シリコンオキシカーバイド負極と対極にリチウム箔を使用し、非水電解質として六フッ化リンリチウムをエチレンカーボネートとジエチルカーボネートの１／１（体積比）混合液に１ｍｏｌ／Ｌの濃度で溶解した非水電解質溶液を用い、セパレータに厚さ３０μｍのポリエチレン製微多孔質フィルムを用いた評価用リチウムイオン二次電池ハーフセルを作製した。
[Comparative Test Example 1]
A slurry was prepared by adding 10 parts of acetylene black, 10 parts of polyvinylidene fluoride, and 150 parts of NMP to 80 parts of the lithium-containing silicon oxycarbide particles obtained in the comparative example. Next, the slurry was applied to a copper foil having a thickness of 18 μm to produce a negative electrode containing lithium-containing silicon oxycarbide. A non-aqueous electrolyte solution in which lithium phosphide was dissolved in a 1/1 (volume ratio) mixture of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / L was used, and a polyethylene microporous film having a thickness of 30 μm was used as the separator. A lithium ion secondary battery half cell for evaluation was produced.
得られたハーフセルを１２時間室温で放置した後、二次電池充放電試験装置（北斗電工）を用いて、初回の充放電容量および初回クーロン効率を評価した。結果を表３に示す。 After the obtained half cell was allowed to stand at room temperature for 12 hours, the initial charge / discharge capacity and the initial coulomb efficiency were evaluated using a secondary battery charge / discharge test apparatus (Hokuto Denko). The results are shown in Table 3.
比較試験例に比して、不可逆容量の低減と初回クーロン効率の向上を確認した。
さらに、本発明の負極活物質は金属リチウムを含まずに上記の優れた初回の充放電容量および初回クーロン効率を得ているため、実用場面で要求される特性を満足しつつ、作業安全性が改善され、水系バインダーも使用可能な優れた活物質であることが分かる。
Compared with the comparative test example, the reduction of the irreversible capacity and the improvement of the initial coulomb efficiency were confirmed.
Furthermore, since the negative electrode active material of the present invention has the above-mentioned excellent initial charge / discharge capacity and initial coulomb efficiency without containing metallic lithium, it satisfies the characteristics required in practical situations, and has work safety. It can be seen that this is an excellent active material that can be improved and a water-based binder can also be used.
Claims (12)
工程（１）により得られたアルカリ金属含有シリコンオキシカーバイドを、アルコール、水及び酸性溶液からなる群より選ばれる少なくとも１種で洗浄処理する工程（２）を含むことを特徴とする非水電解質二次電池用負極活物質の製造方法。 Mixing silicon oxycarbide with an alkali metal source containing at least one selected from the group consisting of alkali metals and alkali metal compounds to obtain an alkali metal-containing silicon oxycarbide (1);
A non-aqueous electrolyte 2 comprising a step (2) of washing the alkali metal-containing silicon oxycarbide obtained in the step (1) with at least one selected from the group consisting of alcohol, water and an acidic solution. The manufacturing method of the negative electrode active material for secondary batteries.
工程（１）で得られたアルカリ金属含有シリコンオキシカーバイドを酸素雰囲気又は窒素雰囲気中で加熱する工程（２）を含むことを特徴とする非水電解質二次電池用負極活物質の製造方法。 Mixing silicon oxycarbide with an alkali metal source containing at least one selected from the group consisting of alkali metals and alkali metal compounds to obtain an alkali metal-containing silicon oxycarbide (1);
A method for producing a negative electrode active material for a nonaqueous electrolyte secondary battery, comprising a step (2) of heating the alkali metal-containing silicon oxycarbide obtained in the step (1) in an oxygen atmosphere or a nitrogen atmosphere.
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| JPH10275617A (en) * | 1997-03-25 | 1998-10-13 | Dow Corning Corp | Formation of electrode material for lithium ion battery |
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| JPH10275617A (en) * | 1997-03-25 | 1998-10-13 | Dow Corning Corp | Formation of electrode material for lithium ion battery |
| JP2015125826A (en) * | 2013-12-25 | 2015-07-06 | 信越化学工業株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery and method for producing the same |
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