JP2013241317A - Lithium lanthanum titanium oxide sintered body, solid electrolyte containing the oxide, and lithium air battery and all-solid lithium battery including the solid electrolyte - Google Patents
Lithium lanthanum titanium oxide sintered body, solid electrolyte containing the oxide, and lithium air battery and all-solid lithium battery including the solid electrolyte Download PDFInfo
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- JP2013241317A JP2013241317A JP2012167448A JP2012167448A JP2013241317A JP 2013241317 A JP2013241317 A JP 2013241317A JP 2012167448 A JP2012167448 A JP 2012167448A JP 2012167448 A JP2012167448 A JP 2012167448A JP 2013241317 A JP2013241317 A JP 2013241317A
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- Prior art keywords
- lithium
- titanium oxide
- sintered body
- oxide sintered
- lanthanum titanium
- Prior art date
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- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 17
- 239000007787 solid Substances 0.000 title description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 58
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 37
- 239000007773 negative electrode material Substances 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- LSYIMYXKHWXNBV-UHFFFAOYSA-N lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[La+3].[Ti+4] LSYIMYXKHWXNBV-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 238000005259 measurement Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 238000005245 sintering Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- 229910018136 Li 2 Ti 3 O 7 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013198 LiNiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MXFFFDCTVRIJQO-UHFFFAOYSA-N [Ca].[Mn].[La] Chemical compound [Ca].[Mn].[La] MXFFFDCTVRIJQO-UHFFFAOYSA-N 0.000 description 1
- QIJHMIVMRGJJLR-UHFFFAOYSA-N [Co].[Ba].[La] Chemical compound [Co].[Ba].[La] QIJHMIVMRGJJLR-UHFFFAOYSA-N 0.000 description 1
- ROYOLNQPXVHWNE-UHFFFAOYSA-N [Co].[Ca].[La] Chemical compound [Co].[Ca].[La] ROYOLNQPXVHWNE-UHFFFAOYSA-N 0.000 description 1
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 1
- ZNZPXPQFEOGASM-UHFFFAOYSA-N [Cu].[Ba].[La] Chemical compound [Cu].[Ba].[La] ZNZPXPQFEOGASM-UHFFFAOYSA-N 0.000 description 1
- GGBSNJKBTGTDHJ-UHFFFAOYSA-N [Cu].[La].[Ca] Chemical compound [Cu].[La].[Ca] GGBSNJKBTGTDHJ-UHFFFAOYSA-N 0.000 description 1
- BXYOGFJOZBMQEB-UHFFFAOYSA-N [Cu].[Sr].[La] Chemical compound [Cu].[Sr].[La] BXYOGFJOZBMQEB-UHFFFAOYSA-N 0.000 description 1
- LMFDUTTUPLNGRB-UHFFFAOYSA-N [Mn].[Ba].[La] Chemical compound [Mn].[Ba].[La] LMFDUTTUPLNGRB-UHFFFAOYSA-N 0.000 description 1
- XGPJPLXOIJRLJN-UHFFFAOYSA-N [Mn].[Sr].[La] Chemical compound [Mn].[Sr].[La] XGPJPLXOIJRLJN-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000012856 weighed raw material Substances 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、リチウム一次電池、リチウム二次電池の固体電解質、例えば全固体リチウムイオン電池の固体電解質やリチウム空気電池の固体電解質として利用できるリチウムランタンチタン酸化物焼結体に関する。 The present invention relates to a lithium lanthanum titanium oxide sintered body that can be used as a solid electrolyte of a lithium primary battery or a lithium secondary battery, for example, a solid electrolyte of an all solid lithium ion battery or a solid electrolyte of a lithium air battery.
近年、パソコン、ビデオカメラ、携帯電話等の情報機器や通信装置の急速な普及に伴い、その電源として利用される電池の開発が重要視されている。また、自動車業界においても、電気自動車やハイブリッド自動車の高出力かつ高容量の電池の開発が進められている。これらに利用される各種電池の中で、エネルギー密度と出力が高いことから、リチウムイオン二次電池が注目されている。一般的なリチウムイオン二次電池は、正極活物質層、負極活物質層と、これら正極活物質層と負極活物質の間の電解質から構成される。 In recent years, with the rapid spread of information devices and communication devices such as personal computers, video cameras, and mobile phones, development of batteries that are used as power sources has been regarded as important. Also in the automobile industry, development of batteries with high output and high capacity for electric vehicles and hybrid vehicles is underway. Among various batteries used for these, lithium ion secondary batteries have attracted attention because of their high energy density and output. A typical lithium ion secondary battery includes a positive electrode active material layer, a negative electrode active material layer, and an electrolyte between the positive electrode active material layer and the negative electrode active material.
一方、空気電池は、高容量二次電池として着目されている。特許文献１には空気極側に水溶性電解液を用いたリチウム空気電池が提案されている。このリチウム空気電池は、負極、負極用の有機電解液、固体電解質からなるセパレータ、空気極用の水溶性電解液及び空気極の順に設けられたリチウム空気電池である。固体電解質には、水分、溶存ガス、プロトン（Ｈ＋）、水酸化イオン（ＯＨ−）などを通さない物質が必要となる。 On the other hand, air batteries are attracting attention as high-capacity secondary batteries. Patent Document 1 proposes a lithium-air battery using a water-soluble electrolyte on the air electrode side. This lithium-air battery is a lithium-air battery provided in the order of a negative electrode, an organic electrolyte for the negative electrode, a separator made of a solid electrolyte, a water-soluble electrolyte for the air electrode, and an air electrode. The solid electrolyte requires a substance that does not pass moisture, dissolved gas, proton (H + ), hydroxide ion (OH − ), or the like.
また、全固体リチウムイオン電池は、電解質として固体電解質を用いたリチウムイオン電池である。全固体リチウムイオン電池は、電解液の漏液やガス発生の心配がないため、現在市販されている電解質に有機電解液を用いたリチウムイオン二次電池に代わる電池として注目されている。 The all solid lithium ion battery is a lithium ion battery using a solid electrolyte as an electrolyte. All-solid-state lithium ion batteries are attracting attention as an alternative to lithium ion secondary batteries that use an organic electrolyte as a commercially available electrolyte because there is no risk of electrolyte leakage or gas generation.
前記空気電池や全固体リチウムイオン電池の固体電解質には、リチウムイオン伝導度の高い材料が必要である。このような材料として、リチウムイオン伝導度が高い材料として、リチウムランタンチタン酸化物が注目されている（例えば、特許文献２および３参照）。 The solid electrolyte of the air battery or the all-solid-state lithium ion battery requires a material having high lithium ion conductivity. As such a material, lithium lanthanum titanium oxide has attracted attention as a material having high lithium ion conductivity (see, for example, Patent Documents 2 and 3).
非特許文献１には、リチウムランタンチタン酸化物が７×１０−５Ｓｃｍ−１と高いリチウムイオン伝導度を示すことが報告されている。また、非特許文献２では、リチウムランタンチタン酸化物にＳｉを添加して、ＳｉＯ２濃度を０．５８〜２．８９重量％にすることによりリチウムイオン伝導度が、最大で８．９×１０−５Ｓｃｍ−１（ＳｉＯ２濃度２．３１重量％、測定温度３０℃）に向上すると報告されている。また、特許文献４では、リチウムランタンチタン酸化物にＡｌ２Ｏ３を添加して、Ａｌ２Ｏ３濃度を１１．１重量％にすることによりリチウムイオン伝導度が粒内で伝導度９．３３×１０−４Ｓｃｍ−１、粒界で伝導度２．３８×１０−５Ｓｃｍ−１（測定温度３０℃）に向上すると報告されている。 Non-Patent Document 1 reports that lithium lanthanum titanium oxide exhibits a high lithium ion conductivity of 7 × 10 −5 Scm −1 . Further, in Non-Patent Document 2, by adding Si to lithium lanthanum titanium oxide and setting the SiO 2 concentration to 0.58 to 2.89 wt%, the lithium ion conductivity is 8.9 × 10 10 at the maximum. It is reported to be improved to −5 Scm −1 (SiO 2 concentration 2.31 wt%, measurement temperature 30 ° C.). In Patent Document 4, by addition of Al 2 O 3 to the lithium lanthanum titanium oxide, Al 2 O 3 concentration of lithium ion conductivity in the grains by the 11.1% by weight of conductivity 9.33 It is reported that × 10 −4 Scm −1 , conductivity is improved to 2.38 × 10 −5 Scm −1 (measurement temperature 30 ° C.) at the grain boundary.
電池の高出力化の観点から、よりリチウムイオン伝導度が高い固体電解質材料が求められている。本発明は、測定温度２７℃でリチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を固体電解質材料として提供することを目的としている。 From the viewpoint of increasing the output of a battery, a solid electrolyte material having higher lithium ion conductivity is required. An object of the present invention is to provide a lithium lanthanum titanium oxide sintered body having a measurement temperature of 27 ° C. and a lithium ion conductivity of 3.0 × 10 −4 Scm −1 or more as a solid electrolyte material.
本発明者らは鋭意検討を重ねた結果、粉末Ｘ線回折パターンにおける、以下の式により求められる相対強度を特定値にすることで、測定温度２７℃でリチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることに成功した。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
すなわち、本発明のリチウムランタンチタン酸化物焼結体は、一般式（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＳｒＴｉＯ３、（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＬａ０．５Ｋ０．５ＴｉＯ３、ＬａｘＬｉ２−３ｘＴｉ１−ａＭａＯ３−ａ、Ｓｒｘ−１．５ａＬａａＬｉ１．５−２ｘＴｉ０．５Ｔａ０．５Ｏ３（０．５５≦ｘ≦０．５８５、０≦ａ≦０．２、Ｍ＝Ａｌ、Ｆｅ、Ｇａのいずれか一つまたは二つ以上を含む）で表され、粉末Ｘ線回折パターンにおける、以下の式により求められる相対強度が１１〜７５％であることを特徴とする。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
As a result of intensive studies, the present inventors set the relative intensity obtained by the following formula in the powder X-ray diffraction pattern to a specific value, so that the lithium ion conductivity is 3.0 × 10 at a measurement temperature of 27 ° C. -4 Scm -1 or more succeeded in obtaining a lithium lanthanum titanium oxide sintered body.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak That is, the lithium lanthanum titanium oxide sintered body of the present invention has the general formula (1- a) La x Li 2-3x TiO 3 —aSrTiO 3 , (1-a) La x Li 2-3x TiO 3 —aLa 0.5 K 0.5 TiO 3 , La x Li 2-3x Ti 1-a M a O 3-a, Sr x -1.5a La a Li 1.5-2x Ti 0.5 Ta 0.5 O 3 (0.55 ≦ x ≦ 0.585,0 ≦ a ≦ 0.2, M = Including any one or more of Al, Fe, and Ga), and the relative intensity obtained by the following formula in the powder X-ray diffraction pattern is 11 to 75%.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak
本発明によれば、リチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることができ、リチウムランタンチタン酸化物焼結体を固体電解質材料として用いることができる。よって、リチウム空気電池、全固体リチウム電池の固体電解質として用いることができる。 According to the present invention, a lithium lanthanum titanium oxide sintered body having a lithium ion conductivity of 3.0 × 10 −4 Scm −1 or more can be obtained, and the lithium lanthanum titanium oxide sintered body is used as a solid electrolyte material. Can be used. Therefore, it can be used as a solid electrolyte of a lithium-air battery or an all-solid lithium battery.
また、本発明の固体電解質は、前記リチウムランタンチタン酸化物焼結体を含むことを特徴とする。
更に、本発明のリチウム空気電池は、前記リチウムランタンチタン酸化物焼結体を固体電解質として備えることを特徴とする。
また、本発明の全固体リチウムイオン電池は、前記リチウムランタンチタン酸化物焼結体を固体電解質として備えることを特徴とする。
Moreover, the solid electrolyte of the present invention is characterized by including the lithium lanthanum titanium oxide sintered body.
Furthermore, the lithium-air battery of the present invention is characterized by including the lithium lanthanum titanium oxide sintered body as a solid electrolyte.
Moreover, the all-solid-state lithium ion battery of this invention is equipped with the said lithium lanthanum titanium oxide sintered compact as a solid electrolyte, It is characterized by the above-mentioned.
本発明は、空気電池や全固体リチウムイオン電池用の固体電解質材料として適したリチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることができる。 INDUSTRIAL APPLICABILITY The present invention can provide a lithium lanthanum titanium oxide sintered body having a lithium ion conductivity of 3.0 × 10 −4 Scm −1 or more suitable as a solid electrolyte material for an air battery or an all solid lithium ion battery. .
本発明のリチウムランタンチタン酸化物は、一般式（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＳｒＴｉＯ３、（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＬａ０．５Ｋ０．５ＴｉＯ３、ＬａｘＬｉ２−３ｘＴｉ１−ａＭａＯ３−ａ、Ｓｒｘ−１．５ａＬａａＬｉ１．５−２ｘＴｉ０．５Ｔａ０．５Ｏ３（０．５５≦ｘ≦０．５８５、０≦ａ≦０．２、Ｍ＝Ａｌ、Ｆｅ、Ｇａから選択される少なくとも一種）で表され、粉末Ｘ線回折パターンにおける、以下の式により求められる相対強度が１１〜７５％である固体電解質材料である。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
The lithium lanthanum titanium oxide of the present invention has a general formula (1-a) La x Li 2-3x TiO 3 —aSrTiO 3 , (1-a) La x Li 2-3x TiO 3 —aLa 0.5 K 0. 5 TiO 3, La x Li 2-3x Ti 1-a M a O 3-a, Sr x-1.5a La a Li 1.5-2x Ti 0.5 Ta 0.5 O 3 (0.55 ≦ x ≦ 0.585, 0 ≦ a ≦ 0.2, M = at least one selected from Al, Fe, and Ga), and the relative intensity determined by the following formula in the powder X-ray diffraction pattern is 11 to 11. It is a solid electrolyte material that is 75%.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak
前記の範囲とすることにより、測定温度２７℃でリチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることができる。 By setting it as the said range, the lithium lanthanum titanium oxide sintered compact whose lithium ion conductivity is 3.0 * 10 < -4 > Scm < -1 > or more can be obtained at the measurement temperature of 27 degreeC.
また、好ましくは、リチウムランタンチタン酸化物焼結体の平均粒径は１８μｍ以上である。より好ましくは、上記組成式、平均粒径においてｘ＝０．５７、ａ≦０．０５で表されるリチウムランタンチタン酸化物焼結体である。前記の範囲とすることにより、測定温度２７℃でリチウムイオン伝導度が４．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることができる。 Preferably, the average particle size of the lithium lanthanum titanium oxide sintered body is 18 μm or more. More preferably, it is a lithium lanthanum titanium oxide sintered body represented by x = 0.57 and a ≦ 0.05 in the above composition formula and average particle diameter. By setting it as the said range, the lithium lanthanum titanium oxide sintered compact whose lithium ion conductivity is 4.0x10 < -4 > Scm < -1 > or more at the measurement temperature of 27 degreeC can be obtained.
本発明のリチウムランタンチタン酸化物焼結体の組成（ｘ、ａ）は以下の方法により決定する。リチウムランタンチタン酸化物とＮａ２Ｏ２とＮａＯＨをジルコニア坩堝に入れて、加熱して溶融する。その後放冷し、水とＨＣｌを加えて溶解する。溶解した液分を分取し、Ｔｉについてはアルミニウム還元−硫酸アンモニウム鉄（ＩＩＩ）滴定法により、その他の元素についてはＩＣＰ発光分光法により定量を行った。 The composition (x, a) of the lithium lanthanum titanium oxide sintered body of the present invention is determined by the following method. Lithium lanthanum titanium oxide, Na 2 O 2 and NaOH are put in a zirconia crucible and heated to melt. Then, it is allowed to cool, and water and HCl are added and dissolved. The dissolved liquid was collected, and Ti was quantified by an aluminum reduction-iron ammonium sulfate (III) titration method, and other elements were quantified by ICP emission spectroscopy.
本発明のリチウムランタンチタン酸化物焼結体のリチウムイオン伝導度は、以下の方法により求める。板状（１５ｍｍ×１５ｍｍ×２．５ｍｍ）のリチウムランタンチタン酸化物焼結体の試料表面を＃１５０のダイヤモンド砥石で研磨を行い、仕上げに＃６００のダイヤモンド砥石で研磨を行う。１０ｍｍ×１０ｍｍの大きさに切り取った２枚のろ紙に、１Ｍの塩化リチウム水溶液を染み込ませ、板状のリチウムランタンチタン酸化物を挟むように貼り付ける。インピーダンスアナライザーを用いて測定周波数５〜１３ＭＨｚ、測定温度２７℃でコール・コールプロットを測定し、測定データから粒内、粒界の抵抗値を読み取る。リチウムイオン伝導度は、以下の計算式より求めた。
リチウムイオン伝導度（Ｓｃｍ−１）＝１／(Ｒｂ＋Ｒｇｂ)×（Ｌ／Ｓ）
Ｒｂ：粒内の抵抗値（Ω）
Ｒｇｂ：粒界の抵抗値（Ω）
Ｌ：板状のリチウムランタンチタン酸化物の厚み（ｃｍ）
Ｓ：電極の面積（ｃｍ２）
The lithium ion conductivity of the lithium lanthanum titanium oxide sintered body of the present invention is determined by the following method. The sample surface of the plate-like (15 mm × 15 mm × 2.5 mm) lithium lanthanum titanium oxide sintered body is polished with a # 150 diamond grindstone, and polished with a # 600 diamond grindstone. Two filter papers cut to a size of 10 mm × 10 mm are soaked with 1M lithium chloride aqueous solution and attached so as to sandwich plate-like lithium lanthanum titanium oxide. A Cole-Cole plot is measured using an impedance analyzer at a measurement frequency of 5 to 13 MHz and a measurement temperature of 27 ° C., and the resistance values of the grains and grain boundaries are read from the measurement data. The lithium ion conductivity was obtained from the following calculation formula.
Lithium ion conductivity (Scm −1 ) = 1 / (R b + R gb ) × (L / S)
R b : Resistance value in the grain (Ω)
R gb : Grain boundary resistance (Ω)
L: Thickness (cm) of plate-like lithium lanthanum titanium oxide
S: Area of electrode (cm 2 )
また、本発明のリチウムランタンチタン酸化物焼結体は単相化率９０％以上のリチウムランタンチタン酸化物の焼結体である。なお、単相化率は、以下の方法により定義されるものである。リチウムランタンチタン酸化物焼結体をアルミナ製の乳鉢で粉砕して測定試料とし、粉末Ｘ線回折装置（Ｘ線源：ＣｕＫα線）を用いて測定する。得られた回折パターンのリチウムランタンチタン酸化物と不純物のメインピークの高さから、単相化率を以下の計算式により求める。
単相化率（％）＝Ｉ／（Ｉ＋Ｓ）×１００
Ｉ：リチウムランタンチタン酸化物の２θ＝０〜５０°における最強ピークの高さ
Ｓ：全ての不純物のメインピークの高さの和
The lithium lanthanum titanium oxide sintered body of the present invention is a sintered body of lithium lanthanum titanium oxide having a single phase conversion rate of 90% or more. The single phase conversion rate is defined by the following method. A lithium lanthanum titanium oxide sintered body is pulverized with an alumina mortar to obtain a measurement sample, which is measured using a powder X-ray diffractometer (X-ray source: CuKα ray). From the height of the main peak of lithium lanthanum titanium oxide and impurities in the obtained diffraction pattern, the single phase conversion rate is obtained by the following calculation formula.
Single phase rate (%) = I / (I + S) × 100
I: height of the strongest peak of lithium lanthanum titanium oxide at 2θ = 0 to 50 ° S: sum of heights of main peaks of all impurities
なお、不純物としては、ＴｉＯ２、Ｌａ２Ｏ３、Ｌｉ２Ｔｉ３Ｏ７、Ｌａ２Ｔｉ２Ｏ７などがある。 Examples of impurities include TiO 2 , La 2 O 3 , Li 2 Ti 3 O 7 , La 2 Ti 2 O 7, and the like.
また、本発明のリチウムランタンチタン酸化物焼結体のミラー指数［００１］のピーク高さと、メインピークであるミラー指数［２２０］または［１１０］のピーク高さとの相対強度は以下の方法により定義されるものである。アルミナ製の乳鉢にリチウムランタンチタン酸化物焼結体、リチウムランタンチタン酸化物焼結体と同体積のセルロース系接着剤、アセトン、エタノールを投入し、混合・粉砕して測定試料とし、粉末Ｘ線回折装置を用いて測定する。得られた回折パターンのリチウムランタンチタン酸化物のミラー指数［００１］のピーク高さと、メインピークであるミラー指数［２２０］または［１１０］のピークの高さから、相対強度を以下の計算式により求める。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
なお、一般式（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＳｒＴｉＯ３、（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＬａ０．５Ｋ０．５ＴｉＯ３、ＬａｘＬｉ２−３ｘＴｉ１−ａＭａＯ３−ａ（０．５５≦ｘ≦０．５８５、０≦ａ≦０．２、Ｍ＝Ａｌ、Ｆｅ、Ｇａから選択される少なくとも一種）の場合、メインピークであるミラー指数は［２２０］であり、一般式Ｓｒｘ−１．５ａＬａａＬｉ１．５−２ｘＴｉ０．５Ｔａ０．５Ｏ３（０．５５≦ｘ≦０．５８５、０≦ａ≦０．２）の場合、メインピークであるミラー指数は、［１１０］である。
The relative intensity between the peak height of the Miller index [001] of the lithium lanthanum titanium oxide sintered body of the present invention and the peak height of the Miller index [220] or [110] as the main peak is defined by the following method. It is what is done. Put lithium lanthanum titanium oxide sintered body in the mortar made of alumina, the same volume of cellulose adhesive, acetone, ethanol as the lithium lanthanum titanium oxide sintered body, mix and grind to make a measurement sample, powder X-ray Measure using a diffractometer. From the peak height of the Miller index [001] of the lithium lanthanum titanium oxide of the obtained diffraction pattern and the peak height of the Miller index [220] or [110] as the main peak, the relative intensity is calculated by the following calculation formula. Ask.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak General formula (1-a) La x Li 2-3x TiO 3 -aSrTiO 3 (1-a) La x Li 2-3x TiO 3 -aLa 0.5 K 0.5 TiO 3 , La x Li 2-3x Ti 1-a M a O 3-a (0.55 ≦ x ≦ 0 .585, 0 ≦ a ≦ 0.2, and M = at least one selected from Al, Fe, and Ga), the Miller index as the main peak is [220], and the general formula Sr x−1.5a La In the case of a Li 1.5-2x Ti 0.5 Ta 0.5 O 3 (0.55 ≦ x ≦ 0.585, 0 ≦ a ≦ 0.2), the Miller index as the main peak is [110]. It is.
本発明のリチウムランタンチタン酸化物焼結体の平均粒径（焼結体を構成する、粒界で隔てられる１セクションの寸法）は以下の方法により求めたものである。得られたリチウムランタンチタン酸化物焼結体の表面に白金を蒸着後、走査型電子顕微鏡により一視野に粒子数が１２００個程度となるような倍率で撮影を行う。得られた画像を基に、画像解析式粒度分布測定ソフトウェアを用いて、各結晶粒子を最小の長方形で囲み、直交する二つの軸のうち長い方を粒径として１０００個以上の結晶粒子の粒径を測定し、その平均を粒子の平均子粒径とした。 The average particle diameter of the lithium lanthanum titanium oxide sintered body of the present invention (the size of one section constituting the sintered body and separated by grain boundaries) is determined by the following method. After depositing platinum on the surface of the obtained lithium lanthanum titanium oxide sintered body, photographing is performed with a scanning electron microscope at a magnification such that the number of particles is about 1200 in one field of view. Based on the obtained image, using the image analysis type particle size distribution measurement software, each crystal particle is surrounded by the smallest rectangle, and the longer of the two orthogonal axes is the particle size of 1000 or more crystal particles. The diameter was measured and the average was taken as the average particle size of the particles.
本発明のリチウムランタンチタン酸化物焼結体の製造方法について、以下に一例として述べる。本発明のリチウムランタンチタン酸化物焼結体の製造方法は、組成及び以下の式により求められる相対強度が本発明の範囲内となる製造方法であれば良い。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
The method for producing a lithium lanthanum titanium oxide sintered body of the present invention will be described below as an example. The manufacturing method of the lithium lanthanum titanium oxide sintered compact of this invention should just be a manufacturing method from which the relative intensity calculated | required by a composition and the following formulas is in the range of this invention.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak
本発明のリチウムランタンチタン酸化物焼結体は、例えば、リチウム原料として、水酸化リチウム及び炭酸リチウム等のリチウム化合物、チタン原料として酸化チタン、水酸化チタン、メタチタン酸、オルトチタン酸等のチタン化合物、あるいはこれらの混合物、ランタン原料として酸化ランタン、炭酸ランタン、水酸化ランタンを用いる。その他の元素（Ｓｒ、Ｋ、Ａｌ、Ｆｅ、Ｇａ、Ｔａ）原料も、酸化物、水酸化物、塩化物、炭酸塩等を用いる。これらの混合原料粉の粉砕を行った後、焼成することにより得ることができる。 The lithium lanthanum titanium oxide sintered body of the present invention includes, for example, lithium compounds such as lithium hydroxide and lithium carbonate as lithium raw materials, and titanium compounds such as titanium oxide, titanium hydroxide, metatitanic acid, and orthotitanic acid as titanium raw materials. Alternatively, lanthanum oxide, lanthanum carbonate, or lanthanum hydroxide is used as a mixture or a lanthanum raw material. Other elements (Sr, K, Al, Fe, Ga, Ta) raw materials also use oxides, hydroxides, chlorides, carbonates, and the like. These mixed raw material powders can be obtained by pulverization and firing.
各原料を所望のモル比にて計量する。このとき、組成を０．５５≦ｘ≦０．５８５、０≦ａ≦０．２に制御することにより、ミラー指数［２２０］または［１１０］のピーク高さを請求の範囲内に制御することができる。なお、リチウム原料は、仮焼と焼結の際のリチウム化合物の揮発を考慮して、リチウム原料に対して０〜１５重量％のリチウム原料を過剰添加する。計量した各原料は、ボールミルに投入し、混合・粉砕を行ない（一次粉砕）、一次粉砕原料を得る。分散媒として純水とアルコール（例えばエタノール）の混合溶媒、必要に応じて界面活性剤等の分散媒を加え、粉砕を行なう。 Each raw material is weighed in the desired molar ratio. At this time, by controlling the composition to 0.55 ≦ x ≦ 0.585 and 0 ≦ a ≦ 0.2, the peak height of the Miller index [220] or [110] is controlled within the scope of the claims. Can do. Note that the lithium raw material is excessively added in an amount of 0 to 15% by weight with respect to the lithium raw material in consideration of volatilization of the lithium compound during calcination and sintering. Each measured raw material is put into a ball mill, mixed and pulverized (primary pulverization) to obtain a primary pulverized raw material. A mixed solvent of pure water and alcohol (for example, ethanol) as a dispersion medium, and a dispersion medium such as a surfactant as necessary are pulverized.
続いて一次粉砕原料を乾燥し、一次乾燥粉を得る。乾燥方法には特に制限は無く、例えば、スプレードライヤー乾燥機、或いは流動層乾燥機、或いは転動造粒乾燥機、或いは凍結乾燥機、或いは熱風乾燥機による乾燥を用いることができる。スプレードライヤー乾燥での乾燥条件は、熱風入口温度が２００〜２５０℃、排風温度が９０〜１２０℃である。 Subsequently, the primary pulverized raw material is dried to obtain a primary dry powder. The drying method is not particularly limited, and for example, drying by a spray dryer dryer, a fluidized bed dryer, a rolling granulation dryer, a freeze dryer, or a hot air dryer can be used. Drying conditions for spray dryer drying are such that the hot air inlet temperature is 200 to 250 ° C. and the exhaust air temperature is 90 to 120 ° C.
次いで一次乾燥粉の仮焼を行ない、仮焼粉を得る。仮焼条件としては、酸素雰囲気中、大気中、或いは不活性雰囲気中（窒素雰囲気中や不活性ガス雰囲気中）で１０００〜１２００℃、１〜１２時間にて仮焼を行う。 Next, the primary dry powder is calcined to obtain a calcined powder. As calcination conditions, calcination is performed in an oxygen atmosphere, the air, or an inert atmosphere (in a nitrogen atmosphere or an inert gas atmosphere) at 1000 to 1200 ° C. for 1 to 12 hours.
得られた仮焼粉は、ボールミルに投入し二次粉砕を行ない、二次粉砕原料を得る。分散媒として純水とアルコール（例えばエタノール）の混合溶媒、必要に応じて界面活性剤等の分散媒を加え、粉砕を行なう。粉砕時間は１〜６時間である。粉砕装置は、ウレタンライニングボールミル、ナイロン製ボールミル、或いは天然ゴムライニングボールミルを用いる。 The obtained calcined powder is put into a ball mill and subjected to secondary pulverization to obtain a secondary pulverized raw material. A mixed solvent of pure water and alcohol (for example, ethanol) as a dispersion medium, and a dispersion medium such as a surfactant as necessary are pulverized. The grinding time is 1 to 6 hours. As the grinding device, a urethane lining ball mill, a nylon ball mill, or a natural rubber lining ball mill is used.
続いて二次粉砕材料は一次粉砕原料と同様に乾燥し、二次乾燥粉を得る。乾燥方法は特に制限は無い。例えば、スプレードライヤー乾燥、或いは熱風乾燥機による乾燥を行うことができる。 Subsequently, the secondary pulverized material is dried in the same manner as the primary pulverized raw material to obtain a secondary dry powder. There is no particular limitation on the drying method. For example, spray dryer drying or drying with a hot air dryer can be performed.
得られた二次乾燥粉は、例えば、ＣＩＰ成形、金型成形、キャスティング成形、押し出し成形、グリーンシートキャスティング成形等の成形方法を用い、所望形状に成形を行ない、成形体を得る。金型成形の際の成形条件としては、例えば、成形圧力４００〜１５００ｋｇ／ｃｍ２である。 The obtained secondary dry powder is molded into a desired shape using a molding method such as CIP molding, mold molding, casting molding, extrusion molding, green sheet casting molding, etc., and a molded body is obtained. As molding conditions in the mold molding, for example, the molding pressure is 400 to 1500 kg / cm 2 .
得られた成形体を焼結し、本発明のリチウムランタンチタン酸化物を得る。１０００〜１２００℃、１〜４時間で一次焼結を行った後、１２００〜１４７５℃、４〜２０時間にて二次焼結を行う。前記二次焼結条件の焼結温度を１２００〜１４７５℃にすることにより、ミラー指数［２２０］または［１１０］のピーク高さを請求の範囲内に制御することができ、さらに平均粒径の大きさも制御することができる。 The obtained molded body is sintered to obtain the lithium lanthanum titanium oxide of the present invention. After performing primary sintering at 1000 to 1200 ° C. for 1 to 4 hours, secondary sintering is performed at 1200 to 1475 ° C. for 4 to 20 hours. By setting the sintering temperature of the secondary sintering conditions to 1200 to 1475 ° C., the peak height of the Miller index [220] or [110] can be controlled within the scope of the claims, and the average particle size of The size can also be controlled.
本発明においては、リチウムイオン伝導度が向上する理由は、定かではないが、以下のように考えられる。ミラー指数［２２０］または［１１０］格子面の電子密度が、リチウムイオン伝導度に影響があると考えられる。そのため、以下の式により求められる相対強度を１１〜７５％にすることにより、リチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上のリチウムランタンチタン酸化物焼結体を得ることができると考えられる。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
In the present invention, the reason why the lithium ion conductivity is improved is not clear, but is considered as follows. The electron density of the Miller index [220] or [110] lattice plane is considered to affect the lithium ion conductivity. Therefore, a lithium lanthanum titanium oxide sintered body having a lithium ion conductivity of 3.0 × 10 −4 Scm −1 or more can be obtained by setting the relative strength obtained by the following formula to 11 to 75%. it is conceivable that.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak
全固体リチウムイオン電池
本発明に係る全固体リチウムイオン電池は、正極活物質を含有する正極活物質層と、負極活物質を含有する負極活物質層と、前記正極活物質層及び前記負極活物質層の間に備えられた本発明のリチウムランタンチタン酸化物焼結体からなる固体電解質層からなる。
All Solid Lithium Ion Battery An all solid lithium ion battery according to the present invention includes a positive electrode active material layer containing a positive electrode active material, a negative electrode active material layer containing a negative electrode active material, the positive electrode active material layer, and the negative electrode active material. It consists of the solid electrolyte layer which consists of the lithium lanthanum titanium oxide sintered compact of this invention provided between the layers.
（正極活物質層）
正極活物質層は、例えば、ＬｉＣｏＯ２、ＬｉＭｎＯ２、ＬｉＮｉＭｎ３Ｏ８、ＬｉＶＯ２、ＬｉＣｒＯ２、ＬｉＦｅＰＯ４、ＬｉＣｏＰＯ４、ＬｉＮｉＯ２、ＬｉＮｉ１/３Ｃｏ１/３Ｍｎ１/３Ｏ２等の正極活物質、必要に応じて、導電材、結着材から構成される。導電材としては、例えば、アセチレンブラック、ケッチェンブラック、カーボンファイバー等を挙げることができる。結着材としては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素含有結着材を挙げることができる。
(Positive electrode active material layer)
The positive electrode active material layer is made of, for example, LiCoO 2 , LiMnO 2 , LiNiMn 3 O 8 , LiVO 2 , LiCrO 2 , LiFePO 4 , LiCoPO 4 , LiNiO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2, etc. It is comprised from a positive electrode active material and a conductive material and a binder as needed. Examples of the conductive material include acetylene black, ketjen black, and carbon fiber. Examples of the binder include fluorine-containing binders such as polytetrafluoroethylene (PTFE).
（負極活物質層）
負極活物質層は金属、カーボン、セラミックス等の負極活物質、導電材、結着材より構成される。例えば、金属活物質としては、リチウム、及びリチウム金属を含む合金を挙げることができる。カーボン活物質としては、例えば、メソカーボンマイクロビーズ（ＭＣＭＢ）、高配向性グラファイト（ＨＯＰＧ）、ハードカーボン、ソフトカーボン等を挙げることができる。またセラミックス活物質としてはＬｉ４Ｔｉ５Ｏ１２を挙げることができる。導電材、固体電解質材料及び結着材は、前述の正極活物質層と同様である。
(Negative electrode active material layer)
The negative electrode active material layer is composed of a negative electrode active material such as metal, carbon, and ceramics, a conductive material, and a binder. For example, examples of the metal active material include lithium and an alloy containing lithium metal. Examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon. An example of the ceramic active material is Li 4 Ti 5 O 12 . The conductive material, solid electrolyte material, and binder are the same as those in the positive electrode active material layer described above.
（その他の構成）
本発明に係る全固体リチウムイオン電池は、正極活物質層の集電を行う正極集電体、及び、負極活物質層の集電を行う負極集電体を備えていてもよい。正極集電体の材料は、使用環境に耐えうる材料であれば特に限定されるものではない。例えば、正極集電体の材料としては、ステンレス、アルミニウム、ニッケル、鉄、チタン等、及び前記金属を含む合金、或いは、カーボン等を挙げることができる。負極集電体の材料としては、ステンレス、銅、ニッケル及び前記金属を含む合金、或いは、カーボン等を挙げることができる。
(Other configurations)
The all-solid-state lithium ion battery according to the present invention may include a positive electrode current collector that collects current from the positive electrode active material layer and a negative electrode current collector that collects current from the negative electrode active material layer. The material of the positive electrode current collector is not particularly limited as long as the material can withstand the use environment. For example, examples of the material for the positive electrode current collector include stainless steel, aluminum, nickel, iron, titanium, and the like, alloys containing the metal, and carbon. Examples of the material of the negative electrode current collector include stainless steel, copper, nickel, an alloy containing the metal, and carbon.
空気電池
本発明に係る空気電池は、負極活物質層、本発明のリチウムランタンチタン酸化物焼結体からなる固体電解質、正極活物質層を有し、負極活物質層と固体電解質の間及び正極活物質層と固体電解質の間に電解液を備えることを特徴とする。
Air Battery The air battery according to the present invention has a negative electrode active material layer, a solid electrolyte composed of the lithium lanthanum titanium oxide sintered body of the present invention, a positive electrode active material layer, and between the negative electrode active material layer and the solid electrolyte and the positive electrode An electrolytic solution is provided between the active material layer and the solid electrolyte.
（正極活物質層）
正極活物質層としては、空気電池の正極として機能可能であれば、その形態は特に限定されるものではなく、公知の形態とすることができる。例えば、炭素を含まない多孔質、気体通過性を有し、導電性を有する複合酸化物、例えば、ランタンストロンチウムマンガン系複合酸化物或いはランタンストロンチウムコバルト系複合酸化物、ランタンストロンチウム銅系複合酸化物、ランタンカルシウムマンガン系複合酸化物、ランタンカルシウムコバルト系複合酸化物、ランタンカルシウム銅系複合酸化物、ランタンバリウムマンガン系複合酸化物、ランタンバリウムコバルト系複合酸化物、ランタンバリウム銅系複合酸化物等を挙げることができる。
(Positive electrode active material layer)
As long as it can function as a positive electrode of an air battery, the form will not be specifically limited as a positive electrode active material layer, It can be set as a well-known form. For example, carbon-free porous, gas-permeable and conductive composite oxides such as lanthanum strontium manganese-based composite oxide or lanthanum strontium cobalt-based composite oxide, lanthanum strontium copper-based composite oxide, Lanthanum calcium manganese complex oxide, lanthanum calcium cobalt complex oxide, lanthanum calcium copper complex oxide, lanthanum barium manganese complex oxide, lanthanum barium cobalt complex oxide, lanthanum barium copper complex oxide, etc. be able to.
（負極活物質層）
負極活物質層は、リチウムイオンを放出可能、好ましくは、リチウムイオンを吸蔵及び放出可能活物質である負極活物質が含有されている。負極活物質としては、金属活物質、例えば、リチウム、及びリチウムを含む合金等、及びＬｉ４Ｔｉ５Ｏ１２を挙げることができる。
(Negative electrode active material layer)
The negative electrode active material layer contains a negative electrode active material that can release lithium ions, and preferably is an active material that can occlude and release lithium ions. Examples of the negative electrode active material include a metal active material such as lithium and an alloy containing lithium, and Li 4 Ti 5 O 12 .
（負極活物質層と固体電解質間の電解液）
電解液は、電解質と溶媒より構成される。電解質は、溶媒中でリチウムイオンを形成するものであれば特に限定されない。例えば、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＡｌＣｌ４、LｉＣＦ３ ＳＯ３、ＬｉＳｂＦ６ 等が挙げられる。これら電解質は単独でもよいが組み合わせて使用してもよい。また、溶媒としては、例えば、プロピレンカーボネート、テトラヒドロフラン、ジメチルスルホキシド、γ−ブチロラクトン、１，３−ジオキソラン、４−メチル−１，３−ジオキソラン、１，２−ジメトキシエタン、２−メチルテトラヒドロフラン、スルホラン、ジエチルカーボネート、ジメチルホルムアミド、アセトニトリル、ジメチルカーボネート、エチレンカーボネート等が挙げられる。これら溶媒は、単独でもよいが、組み合わせて使用してもよい。
(Electrolytic solution between negative electrode active material layer and solid electrolyte)
The electrolytic solution is composed of an electrolyte and a solvent. The electrolyte is not particularly limited as long as it forms lithium ions in a solvent. For example, LiPF 6, LiClO 4, LiBF 4, LiAsF 6, LiAlCl 4, LiCF 3 SO 3, LiSbF 6 , and the like. These electrolytes may be used alone or in combination. Examples of the solvent include propylene carbonate, tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, 2-methyltetrahydrofuran, sulfolane, Examples include diethyl carbonate, dimethylformamide, acetonitrile, dimethyl carbonate, and ethylene carbonate. These solvents may be used alone or in combination.
（正極活物質層と固体電解質間の電解液）
正極活物質層と固体電解質間の電解液は、通常の空気電池に用いられる水系電解液や有機電解液を用いることができる。例えば、ＬｉＯＨ水溶液が挙げられる。
(Electrolytic solution between the positive electrode active material layer and the solid electrolyte)
As the electrolytic solution between the positive electrode active material layer and the solid electrolyte, an aqueous electrolytic solution or an organic electrolytic solution used in a normal air battery can be used. For example, LiOH aqueous solution is mentioned.
（その他の構成）
本発明に係る空気電池は、通常、正極活物質層の集電を行う正極集電体、及び、負極活物質層の集電を行う負極集電体を備える。前記集電体の材料は、空気電池の使用時における環境に耐えうる材料であれば特に限定されるものではない。正極集電体の材料としては、例えば、マンガン、コバルト、ニッケル、ルテニウム、ロジウム、銀、イリジウム、白金、金、ステンレス、アルミニウム、鉄、チタン等の金属、及び前記金属を含む合金、及び、カーボン等を挙げることができる。一方、負極集電体の材料としては、例えば、白金、金、ステンレス、銅、ニッケル等の金属、及び前記金属を含む合金、或いは、カーボン等を挙げることができる。
(Other configurations)
The air battery according to the present invention usually includes a positive electrode current collector that collects current from the positive electrode active material layer and a negative electrode current collector that collects current from the negative electrode active material layer. The material of the current collector is not particularly limited as long as it is a material that can withstand the environment when the air battery is used. Examples of the material of the positive electrode current collector include manganese, cobalt, nickel, ruthenium, rhodium, silver, iridium, platinum, gold, stainless steel, aluminum, iron, titanium, and the like, and alloys containing the above metals and carbon. Etc. On the other hand, examples of the material for the negative electrode current collector include metals such as platinum, gold, stainless steel, copper, and nickel, alloys containing the metal, and carbon.
前記の全固体リチウムイオン電池、空気電池は、移動体装置、設備システム装置、バックアップ電源装置に用いることができる。移動体装置としては、例えば自動車、ホークリフト、建設機械、バイク、自転車、ロボット、航空機、船舶、列車、人工衛星等である。設置システム装置としては、例えば水力発電システム、火力発電システム、原子力発電システム、太陽光発電システム、風力発電システム、地熱発電システム、潮流(海流、波力)発電システム等である。バックアップ電源システム装置としては、例えば、構造物（公共施設、商業施設、工場、病院、住宅等）の緊急電源システム装置等である。 The all solid lithium ion battery and the air battery can be used for a mobile device, an equipment system device, and a backup power supply device. Examples of the mobile device include an automobile, a hawk lift, a construction machine, a motorcycle, a bicycle, a robot, an aircraft, a ship, a train, and an artificial satellite. Examples of the installation system device include a hydroelectric power generation system, a thermal power generation system, a nuclear power generation system, a solar power generation system, a wind power generation system, a geothermal power generation system, a tidal current (sea current, wave power) power generation system, and the like. The backup power supply system device is, for example, an emergency power supply system device for a structure (public facility, commercial facility, factory, hospital, house, etc.).
以下、実施例を挙げて本発明をさらに具体的に説明するが、これは単に例示であって、本発明を制限するものではない。
１．リチウムランタンチタン酸化物焼結体の評価方法
（組成式のｘ、ａの決定方法）
リチウムランタンチタン酸化物焼結体とＮａ２Ｏ２とＮａＯＨをジルコニア坩堝に入れて、加熱して溶融する。その後放冷し、水とＨＣｌを加えて溶解する。溶解した液分を分取し、Ｔｉについてはアルミニウム還元−硫酸アンモニウム鉄（ＩＩＩ）滴定法により、その他の元素についてはＩＣＰ発光分光法により定量を行い、一般式（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＳｒＴｉＯ３、（１−ａ）ＬａｘＬｉ２−３ｘＴｉＯ３―ａＬａ０．５Ｋ０．５ＴｉＯ３、ＬａｘＬｉ２−３ｘＴｉ１−ａＭａＯ３−ａ、Ｓｒｘ−１．５ａＬａａＬｉ１．５−２ｘＴｉ０．５Ｔａ０．５Ｏ３（０．５５≦ｘ≦０．５８５、０≦ａ≦０．２、Ｍ＝Ａｌ、Ｆｅ、Ｇａのいずれか一つまたは二つ以上を含む）のｘ、ａの値を決定した。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.
1. Method for evaluating lithium lanthanum titanium oxide sintered body (method for determining x and a in the composition formula)
Lithium lanthanum titanium oxide sintered body, Na 2 O 2 and NaOH are put in a zirconia crucible and heated to melt. Then, it is allowed to cool, and water and HCl are added and dissolved. The dissolved liquid was collected, and Ti was quantified by aluminum reduction-iron ammonium sulfate (III) titration method, and other elements were quantified by ICP emission spectroscopy, and the general formula (1-a) La x Li 2-2 was obtained. 3x TiO 3 -aSrTiO 3, (1 -a) La x Li 2-3x TiO 3 -aLa 0.5 K 0.5 TiO 3, La x Li 2-3x Ti 1-a M a O 3-a, Sr x-1.5a La a Li 1.5-2x Ti 0.5 Ta 0.5 O 3 (0.55 ≦ x ≦ 0.585, 0 ≦ a ≦ 0.2, M = Al, Fe, Ga The value of x, a of any one or two or more was determined.
（リチウムイオン伝導度測定方法）
板状（１５ｍｍ×１５ｍｍ×２．５ｍｍ）のリチウムランタンチタン酸化物焼結体の試料表面を＃１５０のダイヤモンド砥石で研磨を行い、仕上げに＃６００のダイヤモンド砥石で研磨を行った。１０ｍｍ×１０ｍｍの大きさに切り取った２枚のろ紙に、１Ｍの塩化リチウム水溶液を染み込ませ、板状のリチウムランタンチタン酸化物焼結体を挟むように貼り付けた。インピーダンスアナライザー 型式名：４１９２Ａ（ヒューレットパッカード社製）を用いて測定周波数５Ｈｚ〜１３ＭＨｚ、測定温度２７℃でコール・コールプロットを測定し、測定データから粒内、粒界の抵抗値を読み取り、リチウムイオン伝導度を以下の計算式より求めた。
リチウムイオン伝導度（Ｓｃｍ−１）＝１／(Ｒｂ＋Ｒｇｂ)×（Ｌ/Ｓ）
Ｒｂ：粒内の抵抗値（Ω）
Ｒｇｂ：粒界の抵抗値（Ω）
Ｌ：板状のリチウムランタンチタン酸化物の厚み（ｃｍ）
Ｓ：電極の面積（ｃｍ２）
(Lithium ion conductivity measurement method)
The sample surface of the plate-like (15 mm × 15 mm × 2.5 mm) lithium lanthanum titanium oxide sintered body was polished with a # 150 diamond grindstone and finished with a # 600 diamond grindstone. Two filter papers cut to a size of 10 mm × 10 mm were soaked with a 1M lithium chloride aqueous solution and attached so as to sandwich a plate-like lithium lanthanum titanium oxide sintered body. Impedance analyzer Model name: 4192A (manufactured by Hewlett Packard) is used to measure the Cole-Cole plot at a measurement frequency of 5 Hz to 13 MHz and a measurement temperature of 27 ° C. The conductivity was obtained from the following calculation formula.
Lithium ion conductivity (Scm −1 ) = 1 / (R b + R gb ) × (L / S)
R b : Resistance value in the grain (Ω)
R gb : Grain boundary resistance (Ω)
L: Thickness (cm) of plate-like lithium lanthanum titanium oxide
S: Area of electrode (cm 2 )
（単相化率の測定方法）
得られたリチウムランタンチタン酸化物焼結体をアルミナ製の乳鉢で粉砕して測定試料とし、Ｘ線回折装置（Ｘ線源：ＣｕＫα線） 型式名：Ｘ’Ｐａｒｔ−ＰｒｏＭＰＤ(パナリティカル社製)を用いて測定した。得られたＸ線回折パターンより、リチウムランタンチタン酸化物焼結体と不純物のメインピークの高さから、単相化率を以下の計算式により求めた。
単相化率（％）＝Ｉ／（Ｉ＋Ｓ）×１００
Ｉ：リチウムランタンチタン酸化物の２θ＝０〜５０°における最強ピークの高さ
Ｓ：全ての不純物のメインピークの高さの和
(Measurement method of single phase rate)
The obtained lithium lanthanum titanium oxide sintered body was pulverized with an alumina mortar to obtain a measurement sample. X-ray diffractometer (X-ray source: CuKα ray) Model name: X′Part-ProMPD (manufactured by Panalical) It measured using. From the obtained X-ray diffraction pattern, the single phase ratio was determined from the lithium lanthanum titanium oxide sintered body and the height of the main peak of impurities by the following calculation formula.
Single phase rate (%) = I / (I + S) × 100
I: height of the strongest peak of lithium lanthanum titanium oxide at 2θ = 0 to 50 ° S: sum of heights of main peaks of all impurities
（相対強度の測定方法）
アルミナ製の乳鉢にリチウムランタンチタン酸化物焼結体、リチウムランタンチタン酸化物焼結体と同体積のセメダインＣ（セメダイン株式会社製）、アセトン、エタノールを投入し、混合・粉砕して、測定試料とし、Ｘ線回折装置 型式名：Ｘ’Ｐａｒｔ−ＰｒｏＭＰＤ(パナリティカル社製)を用いて測定した。得られたＸ線回折パターンより、リチウムランタンチタン酸化物のミラー指数［００１］のピーク高さと、メインピークであるミラー指数［２２０］または［１１０］のピークの高さから、単相化率を以下の計算式により求めた。
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ
（粒径測定方法）
得られたリチウムランタンチタン酸化物焼結体の表面を、イオンスパッター（株式会社日立サイエンスシステムズ製）により白金を蒸着後、走査型電子顕微鏡 型式名：Ｓ−４７００（株式会社日立ハイテクノロジーズ製）により一視野に粒子数が１２００個程度となるように撮影を行った。
画像解析式粒度分布測定ソフトウェア 型式名：Ｍａｃ−Ｖｉｅｗ Ｖｅｒ．４（株式会社マウンテック製）により結晶粒子を最小の長方形で囲み、直交する二つの軸のうち長い方を粒径として１０００個以上の粒径を測定し、その平均を粒子の平均粒径とした。
(Measurement method of relative intensity)
Samples of lithium lanthanum titanium oxide sintered body, Cemedine C (produced by Cemedine Co., Ltd.), acetone, and ethanol in the same volume as the lithium lanthanum titanium oxide sintered body, mixed, pulverized, and measurement sample And X-ray diffractometer model name: X′Part-ProMPD (manufactured by Panalical). From the obtained X-ray diffraction pattern, from the peak height of the Miller index [001] of lithium lanthanum titanium oxide and the peak height of the Miller index [220] or [110] which is the main peak, It calculated | required with the following formulas.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak (particle size measurement method)
The surface of the obtained lithium lanthanum titanium oxide sintered body was deposited with platinum by ion sputtering (manufactured by Hitachi Science Systems, Ltd.), and then scanned with an electron microscope Model name: S-4700 (manufactured by Hitachi High-Technologies Corporation). Images were taken so that the number of particles was about 1200 in one field of view.
Image analysis type particle size distribution measurement software Model name: Mac-View Ver. 4 (manufactured by Mountec Co., Ltd.) was used to enclose the crystal particles in the smallest rectangle, measure the particle size of 1000 or more with the longer of the two orthogonal axes as the particle size, and the average was taken as the average particle size of the particles .
［実施例１］
１．原料
原料として炭酸リチウム（Ｓｏｃｉｅｄａｄ
Ｑｕｉｍｉｃａ ｙ Ｍｉｎｅｒａ ｄｅ Ｃｈｉｌｅ Ｓ.Ａ.製、純度９９．２％以上）、酸化ランタン（宣興新威利成稀土有限公司製、純度９９．９９％以上）、酸化チタン（東邦チタニウム株式会社製、純度９９．９９％以上）を使用した。ぞれぞれの原料の重量を表１に示し、炭酸リチウムの過剰添加量は７．５重量％とした。
[Example 1]
1. Raw material Lithium carbonate (Sociedad)
Made by Quimica Minera de Chile SA, purity 99.2% or higher, lanthanum oxide (manufactured by Xingxing Xinwei Cheng rare earth Co., Ltd., purity 99.99% or higher), titanium oxide (made by Toho Titanium Co., Ltd., Purity 99.99% or higher) was used. The weight of each raw material is shown in Table 1, and the excessive amount of lithium carbonate added was 7.5% by weight.
２．一次粉砕
ウレタンライニングボールミル（容量２００Ｌ）に、秤量した原料、アルミナメディア（径３ｍｍ）２００ｋｇ、イオン交換水３５Ｌ及びエタノール３５Ｌ投入し、粉砕・混合３０分行った後、１５時間ボールミル内で放置し再度３０分粉砕を行い、一次粉砕粉（混合原料粉）を得た。
2. Primary grinding Weighed raw material, 200 kg of alumina media (diameter 3 mm), 35 L of ion exchange water and 35 L of ethanol into a urethane lining ball mill (capacity 200 L), pulverized and mixed for 30 minutes, then left in the ball mill for 15 hours and again The mixture was pulverized for 30 minutes to obtain primary pulverized powder (mixed raw material powder).
３．一次乾燥
一次粉砕粉をスプレードライヤーにより乾燥を行い、一次乾燥粉を得た。スプレードライヤーの条件は以下である。
原料供給量：１０〜３０Ｌ／ｈ
熱風入口温度：１５０〜２５０℃
排風温度：９０〜１２０℃
3. Primary drying The primary pulverized powder was dried with a spray dryer to obtain primary dried powder. The conditions of the spray dryer are as follows.
Raw material supply amount: 10-30 L / h
Hot air inlet temperature: 150-250 ° C
Exhaust air temperature: 90-120 ° C
４．仮焼
一次乾燥粉をコウジライトムライト材質の匣鉢にいれ、電気炉にて仮焼を行い、仮焼粉を得た。仮焼条件は、大気中、仮焼温度１１５０℃、仮焼時間２時間にて行った。
4). Calcination The primary dry powder was placed in a koji mullite material bowl and calcined in an electric furnace to obtain a calcined powder. The calcining conditions were performed in the air at a calcining temperature of 1150 ° C. and a calcining time of 2 hours.
５．二次粉砕
ウレタンライニングボールミル（容量２００Ｌ）に、仮焼粉７０ｋｇ、ジルコニアメディア（径３ｍｍ）２００ｋｇ、イオン交換水６０Ｌ、分散剤（ポリアクリル酸アンモニウム塩）７００ｇを投入し、粉砕を６時間行った。その後、アクリル樹脂系バインダー４．５ｋｇを投入し、１５分間混合を行い、二次粉砕粉を得た。
5. Secondary grinding 70 kg of calcined powder, 200 kg of zirconia media (diameter 3 mm), 60 L of ion-exchanged water, 700 g of a dispersant (ammonium polyacrylate) were added to a urethane lining ball mill (capacity 200 L), and grinding was performed for 6 hours. . Thereafter, 4.5 kg of an acrylic resin binder was added and mixed for 15 minutes to obtain a secondary pulverized powder.
６．二次乾燥
二次粉砕粉をスプレードライヤーにより乾燥し、二次乾燥粉を得た。スプレードライヤーの条件は以下である。
原料供給量：１０〜３０Ｌ／ｈ
熱風入口温度：２００〜２５０℃
排風温度：９０〜１２０℃
6). Secondary drying Secondary pulverized powder was dried with a spray dryer to obtain secondary dried powder. The conditions of the spray dryer are as follows.
Raw material supply amount: 10-30 L / h
Hot air inlet temperature: 200-250 ° C
Exhaust air temperature: 90-120 ° C
７．成形
二次乾燥粉１５ｇを、金型成形（成形圧力・１０００ｋｇ／ｃｍ２）により４０ｍｍ×４０ｍｍ×厚み３ｍｍの平板状に成形し、成形体を得た。
7). Molding 15 g of the secondary dry powder was molded into a flat plate shape of 40 mm × 40 mm × thickness 3 mm by molding (molding pressure: 1000 kg / cm 2 ) to obtain a molded body.
８．焼結
成形体を電気炉にて、大気中で１１００℃、２時間で一次焼結を行った後、１４６０℃、６時間にて二次焼結を行い、リチウムランタンチタン酸化物焼結体を得た。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
8). Sintering The sintered compact was subjected to primary sintering at 1100 ° C. for 2 hours in the air in an electric furnace, and then secondary sintering was performed at 1460 ° C. for 6 hours to obtain a lithium lanthanum titanium oxide sintered body. Obtained. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例２］
「８．焼結」の１４６０℃を１４１０℃に変更する以外は実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 2]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that 1460 ° C. in “8. Sintering” was changed to 1410 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例３］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 3]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例４］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 4]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例５］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＳｒＣＯ３を３．６６６ｋg添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 5]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1, and 3.666 kg of SrCO 3 was further added. . Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例６］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＳｒＣＯ３を１１．００ｋg添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 6]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1, and 11.00 kg of SrCO 3 was further added. . Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例７］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＦｅ２Ｏ３を１．８８４ｋg添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 7]
The lithium lanthanum titanium oxide sintered body was prepared in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1 and that 1.84 kg of Fe 2 O 3 was further added. Produced. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例８］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＦｅ２Ｏ３を５．６５１ｋg添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 8]
The lithium lanthanum titanium oxide sintered body was changed in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1 and 5.651 kg of Fe 2 O 3 was further added. Produced. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例９］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＳｒＣＯ３を３６．２９ｋｇ、Ｔａ２Ｏ５を５４．８６ｋｇ添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 9]
Lithium lanthanum was prepared in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1 and that 36.29 kg of SrCO 3 and 54.86 kg of Ta 2 O 5 were further added. A titanium oxide sintered body was produced. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［実施例１０］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更し、さらにＳｒＣＯ３を５．３０ｋｇ、Ｔａ２Ｏ５を５４．８６ｋｇ添加した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Example 10]
Lithium lanthanum was prepared in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1 and that 5.30 kg of SrCO 3 and 54.86 kg of Ta 2 O 5 were further added. A titanium oxide sintered body was produced. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例１］
「８．焼結」の１４６０℃を１３５０℃に変更する以外は実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 1]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that 1460 ° C. in “8. Sintering” was changed to 1350 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例２］
「８．焼結」の１４６０℃を１５００℃に変更する以外は実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 2]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that 1460 ° C. in “8. Sintering” was changed to 1500 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例３］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 3]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例４］
実施例１のそれぞれの原料の重量を表１に示したとおりに変更した以外は、実施例１と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 4]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 1 except that the weight of each raw material in Example 1 was changed as shown in Table 1. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例５］
「８．焼結」の１４６０℃を１３５０℃に変更する以外は実施例５と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 5]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 5 except that 1460 ° C. in “8. Sintering” was changed to 1350 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例６］
「８．焼結」の１４６０℃を１３５０℃に変更する以外は実施例７と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 6]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 7 except that 1460 ° C. in “8. Sintering” was changed to 1350 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
［比較例７］
「８．焼結」の１４６０℃を１３５０℃に変更する以外は実施例９と同じ方法でリチウムランタンチタン酸化物焼結体を作製した。得られたリチウムランタンチタン酸化物焼結体の単相化率、相対強度、平均粒径、リチウムイオン伝導度を表２に示す。
[Comparative Example 7]
A lithium lanthanum titanium oxide sintered body was produced in the same manner as in Example 9 except that 1460 ° C. in “8. Sintering” was changed to 1350 ° C. Table 2 shows the single phase conversion rate, relative strength, average particle size, and lithium ion conductivity of the obtained lithium lanthanum titanium oxide sintered body.
表１および２から明らかなように、相対強度が下限値を下回る比較例１、３、５〜７および上限値を上回る比較例２および４は、いずれもリチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１未満であった。一方、いずれの数値も本発明の範囲内である実施例１〜１０は、リチウムイオン伝導度が３．０×１０−４Ｓｃｍ−１以上であった。 As is clear from Tables 1 and 2, Comparative Examples 1, 3, 5 to 7 in which the relative strength is lower than the lower limit and Comparative Examples 2 and 4 in which the relative intensity is higher than the upper limit are all lithium ion conductivity of 3.0 × 10. It was less than -4 Scm- 1 . On the other hand, Examples 1-10 which are all within the scope of the present invention had lithium ion conductivity of 3.0 × 10 −4 Scm −1 or more.
本発明は、リチウム一次電池、リチウム二次電池の固体電解質、例えば全固体リチウムイオン電池の固体電解質やリチウム空気電池の固体電解質として利用できるリチウムランタンチタン酸化物焼結体を提供でき、有望である。
INDUSTRIAL APPLICABILITY The present invention can provide a lithium lanthanum titanium oxide sintered body that can be used as a solid electrolyte of a lithium primary battery or a lithium secondary battery, such as a solid electrolyte of an all-solid lithium ion battery or a solid electrolyte of a lithium air battery, and is promising. .
Claims (8)
相対強度（％）＝Ａ／Ｂ×１００
Ａ：ミラー指数［００１］のピーク高さ
Ｂ：メインピークであるミラー指数［２２０］または［１１０］のピーク高さ General formula (1-a) La x Li 2-3x TiO 3 —aSrTiO 3 , (1-a) La x Li 2-3x TiO 3 —aLa 0.5 K 0.5 TiO 3 , La x Li 2-3x Ti 1-a M a O 3 -a, Sr x-1.5a La a Li 1.5-2x Ti 0.5 Ta 0.5 O 3 (0.55 ≦ x ≦ 0.585,0 ≦ a ≦ 0.2, M = at least one selected from Al, Fe, and Ga), and the relative intensity obtained by the following formula in the powder X-ray diffraction pattern is 11 to 75%. Lanthanum titanium oxide sintered body.
Relative strength (%) = A / B × 100
A: Peak height of Miller index [001] B: Peak height of Miller index [220] or [110] which is the main peak
An all-solid-state lithium ion battery comprising the solid electrolyte according to claim 5.
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