JP7447396B2 - alkali metal ion battery - Google Patents
alkali metal ion battery Download PDFInfo
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- JP7447396B2 JP7447396B2 JP2019029932A JP2019029932A JP7447396B2 JP 7447396 B2 JP7447396 B2 JP 7447396B2 JP 2019029932 A JP2019029932 A JP 2019029932A JP 2019029932 A JP2019029932 A JP 2019029932A JP 7447396 B2 JP7447396 B2 JP 7447396B2
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- Prior art keywords
- negative electrode
- layer
- alkali metal
- metal ion
- solid electrolyte
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- 229910001413 alkali metal ion Inorganic materials 0.000 title claims description 52
- 239000011777 magnesium Substances 0.000 claims description 70
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 63
- 229910052749 magnesium Inorganic materials 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 58
- 239000007773 negative electrode material Substances 0.000 claims description 39
- 238000007600 charging Methods 0.000 claims description 38
- 239000007784 solid electrolyte Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 26
- 239000002203 sulfidic glass Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000006258 conductive agent Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 127
- 239000000463 material Substances 0.000 description 49
- 229910052751 metal Inorganic materials 0.000 description 41
- 239000002184 metal Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 36
- 229910001416 lithium ion Inorganic materials 0.000 description 29
- 239000003575 carbonaceous material Substances 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000007599 discharging Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011255 nonaqueous electrolyte Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000003701 mechanical milling Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 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
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018111 Li 2 S-B 2 S 3 Inorganic materials 0.000 description 1
- 229910018127 Li 2 S-GeS 2 Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910007919 Li-Ba Inorganic materials 0.000 description 1
- 229910007912 Li-Cd Inorganic materials 0.000 description 1
- 229910007975 Li-Ga Inorganic materials 0.000 description 1
- 229910008029 Li-In Inorganic materials 0.000 description 1
- 229910008367 Li-Pb Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008414 Li-Sr Inorganic materials 0.000 description 1
- 229910008405 Li-Zn Inorganic materials 0.000 description 1
- 229910009324 Li2S-SiS2-Li3PO4 Inorganic materials 0.000 description 1
- 229910009320 Li2S-SiS2-LiBr Inorganic materials 0.000 description 1
- 229910009316 Li2S-SiS2-LiCl Inorganic materials 0.000 description 1
- 229910009318 Li2S-SiS2-LiI Inorganic materials 0.000 description 1
- 229910009328 Li2S-SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007281 Li2S—SiS2—B2S3LiI Inorganic materials 0.000 description 1
- 229910007295 Li2S—SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007291 Li2S—SiS2—LiBr Inorganic materials 0.000 description 1
- 229910007288 Li2S—SiS2—LiCl Inorganic materials 0.000 description 1
- 229910007289 Li2S—SiS2—LiI Inorganic materials 0.000 description 1
- 229910007306 Li2S—SiS2—P2S5LiI Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910008299 Li—Cd Inorganic materials 0.000 description 1
- 229910006620 Li—Ga Inorganic materials 0.000 description 1
- 229910006670 Li—In Inorganic materials 0.000 description 1
- 229910006738 Li—Pb Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910007049 Li—Zn Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108091006595 SLC15A3 Proteins 0.000 description 1
- 102100021485 Solute carrier family 15 member 3 Human genes 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910000946 Y alloy Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
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- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite 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
Description
本発明は、アルカリ金属イオン電池に関する。 The present invention relates to an alkali metal ion battery.
リチウムイオン非水電解質二次電池に代表される非水電解質二次電池は、エネルギー密度の高さから、パーソナルコンピュータ、通信端末等の電子機器、自動車等に多用されている。上記非水電解質二次電池は、一般的には、電気的に隔離された一対の電極を有する電極体、及び電極間に介在する非水電解質を備え、両電極間でイオンの受け渡しを行うことで充放電するよう構成される。 Nonaqueous electrolyte secondary batteries, typified by lithium ion nonaqueous electrolyte secondary batteries, have high energy density and are widely used in electronic devices such as personal computers and communication terminals, automobiles, and the like. The non-aqueous electrolyte secondary battery generally includes an electrode body having a pair of electrically isolated electrodes and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the two electrodes. The battery is configured to be charged and discharged.
近年、理論容量が大きく体積膨張率が小さいマグネシウムが着目されている。従来技術においては、マグネシウム等を含む金属複合酸化物からなる負極活物質を用いた高容量でエネルギー密度が高いリチウムイオン二次電池が提案されている（特許文献１参照）。 In recent years, magnesium, which has a large theoretical capacity and a small volumetric expansion coefficient, has attracted attention. In the prior art, a lithium ion secondary battery with high capacity and high energy density using a negative electrode active material made of a metal composite oxide containing magnesium or the like has been proposed (see Patent Document 1).
しかしながら、ハイブリッド電気自動車（以下、「ＨＥＶ」ともいう。）やハイブリッド式の産業機械（重機、建機等）に用いられる非水電解質二次電池等の蓄電素子においては、放電容量のさらなる向上が望まれる。 However, further improvement in discharge capacity is required for energy storage elements such as non-aqueous electrolyte secondary batteries used in hybrid electric vehicles (hereinafter also referred to as "HEV") and hybrid industrial machinery (heavy machinery, construction machinery, etc.). desired.
本発明は、以上のような事情に基づいてなされたものであり、放電容量が良好なアルカリ金属イオン電池の提供を目的とする。 The present invention was made based on the above circumstances, and aims to provide an alkali metal ion battery with good discharge capacity.
非水電解質リチウムイオン電池における金属マグネシウム負極は、非水電解質としてエチレンカーボネート（ＥＣ）及びジメチルカーボネート（ＤＭＣ）を１：２の体積比で混合した溶媒にリチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を１ｍｏｌ／ｄｍ３の濃度で溶解させた非水電解液を用いた場合には、Ｌｉ＋イオンと可逆的な反応を示さず、あらかじめ金属マグネシウムが金属Ｌｉと合金化されたＬｉｘＭｇ（ｘ≧０．６）合金を負極に用いることでＬｉ＋イオンと可逆的な反応が起こることが報告されている（Ｊｏｕｒｎａｌ ｏｆ Ｐｏｗｅｒ Ｓｏｕｒｃｅｓ，２００１，Ｖｏｌ９２，７０－８０）。 The metal magnesium negative electrode in a nonaqueous electrolyte lithium ion battery is produced by adding lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to a solvent containing a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) at a volume ratio of 1:2 as a nonaqueous electrolyte. When using a non-aqueous electrolyte in which Li + ions are dissolved at a concentration of 1 mol/ dm3 , LixMg (x≧0 .6) It has been reported that a reversible reaction with Li + ions occurs when the alloy is used as a negative electrode (Journal of Power Sources, 2001, Vol. 92, 70-80).
そこで、本発明者らは、非水電解液由来の析出物による被膜が金属マグネシウム負極の表面に形成されることにより、金属マグネシウム負極とＬｉ＋イオンとの反応が阻害されており、この非水電解液由来の析出物を抑制することで金属マグネシウム負極とＬｉ＋イオンとの反応が阻害されることがなくなり、放電容量を向上できるのではないかと考え、本発明に至った。 Therefore, the present inventors discovered that the reaction between the metal magnesium negative electrode and Li + ions is inhibited by the formation of a film of precipitates derived from the non-aqueous electrolyte on the surface of the metal magnesium negative electrode. The present invention was developed based on the idea that by suppressing the precipitates derived from the electrolytic solution, the reaction between the metal magnesium negative electrode and Li + ions would not be inhibited, and the discharge capacity could be improved.
上記課題を解決するためになされた本発明の一態様は、マグネシウムを含む負極と、硫化物固体電解質とを備えるアルカリ金属イオン電池である。 One aspect of the present invention made to solve the above problems is an alkali metal ion battery that includes a negative electrode containing magnesium and a sulfide solid electrolyte.
本発明によれば、放電容量が良好なアルカリ金属イオン電池を得ることができる。 According to the present invention, an alkali metal ion battery with good discharge capacity can be obtained.
本発明の一態様に係るアルカリ金属イオン電池は、マグネシウムを含む負極と、硫化物固体電解質とを備えるアルカリ金属イオン電池である。 An alkali metal ion battery according to one embodiment of the present invention is an alkali metal ion battery that includes a negative electrode containing magnesium and a sulfide solid electrolyte.
当該アルカリ金属イオン電池が、マグネシウムを含む負極と、硫化物固体電解質とを備えることで、放電容量及び充放電効率を向上できる。この理由については定かでは無いが、以下の理由が推測される。上述したように、金属マグネシウム負極を備える一般的な非水電解液リチウムイオン二次電池の場合、金属マグネシウム負極とＬｉ＋イオンとの反応が起こりにくいことが知られている。これは、初回充電時に非水電解液由来の析出物による被膜が金属マグネシウム負極の表面に形成されることにより、金属マグネシウム負極とＬｉ＋イオンとの反応が阻害されることによると考えられる。当該アルカリ金属イオン電池は、マグネシウムを含む負極と、硫化物固体電解質とを備えることで、マグネシウムを含む負極の表面に非水電解液由来の析出物による被膜が形成されることがない。その結果、金属マグネシウム負極とＬｉ＋イオンとの間で可逆的な反応が抑制されず、放電容量及び充放電効率を向上できると推察される。 When the alkali metal ion battery includes a negative electrode containing magnesium and a sulfide solid electrolyte, discharge capacity and charge/discharge efficiency can be improved. Although the reason for this is not certain, the following reasons are presumed. As mentioned above, in the case of a general non-aqueous electrolyte lithium ion secondary battery equipped with a metallic magnesium negative electrode, it is known that a reaction between the metallic magnesium negative electrode and Li + ions is difficult to occur. This is considered to be because a film of precipitates derived from the non-aqueous electrolyte is formed on the surface of the metal magnesium negative electrode during the first charge, thereby inhibiting the reaction between the metal magnesium negative electrode and Li + ions. Since the alkali metal ion battery includes a negative electrode containing magnesium and a sulfide solid electrolyte, a film of precipitates derived from a non-aqueous electrolyte is not formed on the surface of the negative electrode containing magnesium. As a result, it is presumed that the reversible reaction between the metal magnesium negative electrode and Li + ions is not suppressed, and the discharge capacity and charge/discharge efficiency can be improved.
上記負極が、ＡＸＭｇＹＭＺ（Ａは、アルカリ金属元素である。Ｍは、Ｍｇと合金を形成可能なＡ以外の金属元素である。１＞Ｘ≧０、１≧Ｙ＞０、０．３≧Ｚ≧０、Ｘ＋Ｙ＋Ｚ＝１）を含むことが好ましい。上記負極が、上記ＡＸＭｇＹＭＺを含むことで、放電容量及び充放電効率を高めることができる。 The above - mentioned negative electrode is A 0.3≧Z≧0, X+Y+Z=1). When the negative electrode contains the A X Mg Y M Z , the discharge capacity and charge/discharge efficiency can be increased.
上記負極が、表面上にＭｇＳを含有する被膜を備えることが好ましい。上記被膜は、硫化物固体電解質中の硫黄と負極に含まれるマグネシウムとの反応によるものである。金属マグネシウムは、還元力が強いことから負極と硫化物固体電解質との界面にＭｇＳが形成されやすいと推察される。このＭｇＳは、他の固体電解質との界面に形成されるＭｇＯ等と比較してバンドギャップが狭く、電気伝導度に優れていると考えられることから、界面抵抗の上昇が抑制され、金属マグネシウムの絶縁化が軽減されて放電容量及び充放電効率をより高めることができると推察される。 It is preferable that the negative electrode has a coating containing MgS on its surface. The above film is formed by a reaction between sulfur in the sulfide solid electrolyte and magnesium contained in the negative electrode. Since metallic magnesium has a strong reducing power, it is presumed that MgS is likely to be formed at the interface between the negative electrode and the sulfide solid electrolyte. This MgS has a narrower bandgap and is thought to have superior electrical conductivity compared to MgO, etc., which is formed at the interface with other solid electrolytes, so it suppresses the increase in interfacial resistance and makes the metal magnesium It is inferred that insulation is reduced and discharge capacity and charge/discharge efficiency can be further enhanced.
上記負極が、炭素材料を含むことが好ましい。 It is preferable that the negative electrode contains a carbon material.
上記負極が、上記炭素材料を含むことで、放電容量及び充放電効率を高めることができる。この理由については定かでは無いが、以下の理由が推測される。炭素材料とＬｉ＋イオンとの反応（炭素材料へのＬｉ挿入）電位は、金属マグネシウムとＬｉ＋イオンとの反応電位よりも貴であるために、当該アルカリ金属イオン電池における充電反応では、マグネシウムを含む負極において炭素材料へのＬｉ挿入が生じた後に、マグネシウムを含む負極活物質とＬｉ＋イオンとが反応すると考えられる。ここで、硫化物固体電解質－マグネシウムを含む負極活物質間でのＬｉ移動に伴う抵抗よりも、硫化物固体電解質－炭素材料間、及び炭素材料－マグネシウムを含む負極活物質間でのＬｉ移動に伴う抵抗の方が小さいと考えられる。その結果、マグネシウムを含む負極とＬｉ＋イオンとの反応抵抗が小さくなり、放電容量及び充放電効率を向上できると推察される。 When the negative electrode contains the carbon material, discharge capacity and charge/discharge efficiency can be increased. Although the reason for this is not certain, the following reasons are presumed. The reaction potential between carbon material and Li + ions (Li insertion into carbon material) is nobler than the reaction potential between metal magnesium and Li + ions, so in the charging reaction in the alkali metal ion battery, magnesium is It is considered that after Li insertion into the carbon material occurs in the negative electrode containing magnesium, the negative electrode active material containing magnesium reacts with Li + ions. Here, the resistance due to Li transfer between the sulfide solid electrolyte and the negative electrode active material containing magnesium is greater than the resistance due to Li transfer between the sulfide solid electrolyte and the carbon material and between the carbon material and the negative electrode active material containing magnesium. The associated resistance is considered to be smaller. As a result, it is presumed that the reaction resistance between the magnesium-containing negative electrode and Li + ions is reduced, and the discharge capacity and charge/discharge efficiency can be improved.
以下、本発明に係るアルカリ金属イオン電池の実施形態について詳説する。 Hereinafter, embodiments of the alkali metal ion battery according to the present invention will be described in detail.
＜アルカリ金属イオン電池＞
図１は、本発明の一実施形態におけるアルカリ金属イオン電池１０を示す模式的断面図である。二次電池であるアルカリ金属イオン電池１０は、少なくとも負極層１と、正極層２とが固体電解質層３を介して配置される。負極層１は、負極基材層４及び負極合剤層５を有し、負極基材層４が負極層１の最外層となる。正極層２は、正極基材層７及び正極合剤層６を有し、正極基材層７が正極層２の最外層となる。図１に示すアルカリ金属イオン電池１０においては、正極基材層７上に、正極合剤層６、固体電解質層３、負極合剤層５及び負極基材層４がこの順で積層されている。
<Alkali metal ion battery>
FIG. 1 is a schematic cross-sectional view showing an alkali metal ion battery 10 in one embodiment of the present invention. In an alkali metal ion battery 10 that is a secondary battery, at least a negative electrode layer 1 and a positive electrode layer 2 are arranged with a solid electrolyte layer 3 in between. The negative electrode layer 1 has a negative electrode base material layer 4 and a negative electrode mixture layer 5, and the negative electrode base material layer 4 is the outermost layer of the negative electrode layer 1. The positive electrode layer 2 has a positive electrode base material layer 7 and a positive electrode mixture layer 6, and the positive electrode base material layer 7 is the outermost layer of the positive electrode layer 2. In the alkali metal ion battery 10 shown in FIG. 1, a positive electrode mixture layer 6, a solid electrolyte layer 3, a negative electrode mixture layer 5, and a negative electrode base material layer 4 are laminated in this order on a positive electrode base material layer 7. .
＜負極層＞
負極層１は、負極基材層４と、この負極基材層４の表面に積層される負極合剤層５とを備える。また、負極層１は負極基材層４と負極合剤層５との間に図示しない中間層を有していてもよい。以下、負極層１の各構成要素について詳細に説明する。
<Negative electrode layer>
The negative electrode layer 1 includes a negative electrode base material layer 4 and a negative electrode mixture layer 5 laminated on the surface of the negative electrode base material layer 4. Further, the negative electrode layer 1 may have an intermediate layer (not shown) between the negative electrode base material layer 4 and the negative electrode mixture layer 5. Each component of the negative electrode layer 1 will be described in detail below.
［負極基材層］
負極基材層４は導電性を有する層である。負極基材層４の材質としては、導電体であればどのようなものでもよく、例えば、銅、アルミニウム、チタン、ニッケル、タンタル、ニオブ、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモン、金、銀、鉄、白金、クロム、スズ、インジウム及びこれらの一種以上を含む合金並びにステンレス合金からなる群から選択される一種以上の金属、炭素、導電性高分子、導電性ガラス等を挙げることができる。
[Negative electrode base material layer]
The negative electrode base material layer 4 is a layer having electrical conductivity. The material of the negative electrode base layer 4 may be any conductor, such as copper, aluminum, titanium, nickel, tantalum, niobium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, gold, Examples include one or more metals selected from the group consisting of silver, iron, platinum, chromium, tin, indium, alloys containing one or more of these, and stainless steel alloys, carbon, conductive polymers, conductive glass, etc. .
負極基材層４の平均厚さの下限としては、３μｍが好ましく、５μｍがより好ましく、８μｍがさらに好ましい。一方、負極基材層４の平均厚さの上限としては、２００μｍが好ましく、１００μｍがより好ましく、５０μｍがさらに好ましい。負極基材層４の平均厚さが前記下限以上とすることで、負極基材層４の強度を十分に高くできるため、負極層１を良好に形成できる。負極基材層４の平均厚さを前記上限以下とすることで、他の構成要素の体積を十分に確保できる。 The lower limit of the average thickness of the negative electrode base material layer 4 is preferably 3 μm, more preferably 5 μm, and even more preferably 8 μm. On the other hand, the upper limit of the average thickness of the negative electrode base material layer 4 is preferably 200 μm, more preferably 100 μm, and even more preferably 50 μm. By setting the average thickness of the negative electrode base material layer 4 to be equal to or greater than the lower limit, the strength of the negative electrode base material layer 4 can be sufficiently increased, so that the negative electrode layer 1 can be formed satisfactorily. By setting the average thickness of the negative electrode base material layer 4 to be equal to or less than the above upper limit, a sufficient volume of other components can be ensured.
［負極合剤層］
負極合剤層５は、負極活物質を含むいわゆる負極合剤から形成することができる。負極合剤は、マグネシウムを含む負極活物質を含有する。負極合剤は、必要に応じて導電剤、バインダー、フィラー等の任意成分を含む。
[Negative electrode mixture layer]
The negative electrode mixture layer 5 can be formed from a so-called negative electrode mixture containing a negative electrode active material. The negative electrode mixture contains a negative electrode active material containing magnesium. The negative electrode mixture contains optional components such as a conductive agent, a binder, and a filler as necessary.
（負極活物質）
マグネシウムを含む負極活物質は、マグネシウムを含み、アルカリ金属イオンを吸蔵及び放出することができる材質が用いられる。負極活物質としては、ＡＸＭｇＹＭＺを含むことが好ましい。ここで、Ａは、アルカリ金属元素である。Ｍは、Ｍｇと合金を形成可能なＡ以外の金属元素である。また、１＞Ｘ≧０、１≧Ｙ＞０、０．３≧Ｚ≧０かつＸ＋Ｙ＋Ｚ＝１である。
(Negative electrode active material)
For the negative electrode active material containing magnesium, a material containing magnesium and capable of occluding and releasing alkali metal ions is used. The negative electrode active material preferably contains A X Mg Y M Z. Here, A is an alkali metal element. M is a metal element other than A that can form an alloy with Mg. Further, 1>X≧0, 1≧Y>0, 0.3≧Z≧0, and X+Y+Z=1.
Ａで表されるアルカリ金属元素としては、例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ等が挙げられる。これらの中では、エネルギー密度が高く、容易に高電圧を得られる観点からＬｉが好ましい。上記Ａは、最初から負極に含まれる場合と充電時において吸蔵される場合がある。負極活物質に、正極活物質から放出されるアルカリ金属イオンＡ１と異なるアルカリ金属元素Ａ２が含まれる場合、Ａ２は、Ａ１Ｘ１ＭｇＹからＡ１が脱離する反応電位よりも卑な電位で、Ａ２Ｘ２ＭｇＹから脱離する元素であることが好ましく、Ａ２Ｘ２ＭｇＹから脱離しない元素であることも好ましい。 Examples of the alkali metal element represented by A include Li, Na, K, Rb, and Cs. Among these, Li is preferred because it has a high energy density and can easily obtain a high voltage. The above A may be included in the negative electrode from the beginning or occluded during charging. When the negative electrode active material contains an alkali metal element A2 different from the alkali metal ion A1 released from the positive electrode active material, A2 is a potential less base than the reaction potential at which A1 is desorbed from A1 It is preferable that it is an element that is desorbed from X2 Mg Y , and it is also preferable that it is an element that is not desorbed from A2 X2 Mg Y.
ＡがＬｉの場合、Ｘ／（Ｘ＋Ｙ）≧０．２が好ましい。ＬｉＸＭｇＹの固相内リチウムイオン拡散は、ＬｉＸＭｇＹが体心立方構造（β相）（Ｘ／（Ｘ＋Ｙ）≧０．３）のときに比べて、ＬｉＸＭｇＹが六方細密構造（α相）（Ｘ／（Ｘ＋Ｙ）≦０．２）のときに低くなるためである。なお、充放電前にはＬｉを含まない金属マグネシウムを負極活物質として用いた場合であっても、充放電後にはＬｉＸＭｇＹ（Ｘ／（Ｘ＋Ｙ）≧０．２）となる場合がある。 When A is Li, it is preferable that X/(X+Y)≧0.2. The lithium ion diffusion in the solid phase of Li This is because it becomes low when the structure (α phase) (X/(X+Y)≦0.2). Note that even if metal magnesium that does not contain Li is used as a negative electrode active material before charging and discharging, Li X Mg Y (X/(X+Y)≧0.2) may occur after charging and discharging. .
ＬｉＸＭｇＹにおいてＸ／（Ｘ＋Ｙ）≧０．２とする方法は特に限定されないが、例えば、負極合剤層上に金属リチウムを成膜してもよく、当該アルカリ金属イオン電池の製造工程において、負極とリチウムイオンとを反応させる充電工程を実施してもよい。 The method for setting X/(X+ Y )≧ 0.2 in Li , a charging step may be performed in which the negative electrode and lithium ions are reacted.
Ｍで表されるＭｇと合金を形成可能なＡ以外の金属元素としては、例えばＡｌ、Ｚｎ、Ａｇ、Ｎｉ、Ｃｕ、Ｔｈ等が挙げられる。これらの中では、質量エネルギー密度の観点からＡｌが好ましい。 Examples of metal elements other than A that can form an alloy with Mg, which is represented by M, include Al, Zn, Ag, Ni, Cu, and Th. Among these, Al is preferred from the viewpoint of mass energy density.
具体的なマグネシウムを含む負極活物質としては、例えば金属マグネシウム、Ｌｉ０．２Ｍｇ０．８、Ｌｉ０．１４Ｍｇ０．５６Ａｌ０．３等が挙げられる。これらの中では、金属マグネシウムが好ましい。 Specific examples of the negative electrode active material containing magnesium include metal magnesium, Li 0.2 Mg 0.8 , Li 0.14 Mg 0.56 Al 0.3 , and the like. Among these, metal magnesium is preferred.
マグネシウムを含む負極活物質の平均粒径は、例えば、０．０１μｍ以上２００μｍ以下としてもよい。これらの中でも、平均粒径の上限は１５０μｍが好ましく、１００μｍがより好ましく、５０μｍがさらに好ましい。平均粒径の下限は、０．１μｍが好ましく、０．５μｍがより好ましく、１μｍがさらに好ましい。
マグネシウムを含む負極活物質の平均粒径を前記のようにすることで、放電容量及び充放電効率を向上できる。
The average particle size of the negative electrode active material containing magnesium may be, for example, 0.01 μm or more and 200 μm or less. Among these, the upper limit of the average particle diameter is preferably 150 μm, more preferably 100 μm, and even more preferably 50 μm. The lower limit of the average particle size is preferably 0.1 μm, more preferably 0.5 μm, and even more preferably 1 μm.
By setting the average particle size of the negative electrode active material containing magnesium as described above, discharge capacity and charge/discharge efficiency can be improved.
本明細書において、「平均粒径」とは、特に断りがない場合ＪＩＳ－Ｚ－８８２５（２０１３年）に準拠し、粒子を溶媒で希釈した希釈液に対しレーザ回折・散乱法により測定した粒径分布に基づき、ＪＩＳ－Ｚ－８８１９－２（２００１年）に準拠し計算される体積基準積算分布が５０％となる値を意味する。 In this specification, "average particle size" refers to the particle size measured by laser diffraction/scattering method on a diluted solution in which particles are diluted with a solvent, in accordance with JIS-Z-8825 (2013), unless otherwise specified. It means a value at which the volume-based cumulative distribution calculated in accordance with JIS-Z-8819-2 (2001) is 50% based on the diameter distribution.
負極合剤は、マグネシウムを含む負極活物質に加えて、炭素材料から成る負極活物質を含むことが好ましい。 The negative electrode mixture preferably contains a negative electrode active material made of a carbon material in addition to a negative electrode active material containing magnesium.
炭素材料から成る負極活物質としては、例えば、黒鉛（グラファイト）、非黒鉛質炭素（易黒鉛化性炭素又は難黒鉛化性炭素）等が挙げられる。これらの中でも黒鉛が好ましい。 Examples of the negative electrode active material made of a carbon material include graphite, non-graphitic carbon (easily graphitizable carbon or non-graphitizable carbon), and the like. Among these, graphite is preferred.
「黒鉛」とは、充放電前又は放電状態において、Ｘ線回折法により決定される（００２）面の平均格子面間隔（ｄ００２）が０．３３ｎｍ以上０．３４ｎｍ未満の炭素材料をいう。黒鉛としては、天然黒鉛、人造黒鉛が挙げられる。安定した物性の材料を入手できるという観点で、人造黒鉛が好ましい。 "Graphite" refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane of 0.33 nm or more and less than 0.34 nm before charging and discharging or in a discharge state, as determined by X-ray diffraction. Examples of graphite include natural graphite and artificial graphite. Artificial graphite is preferred from the viewpoint of being able to obtain a material with stable physical properties.
「非黒鉛質炭素」とは、充放電前又は放電状態においてＸ線回折法により決定される（００２）面の平均格子面間隔（ｄ００２）が０．３４ｎｍ以上０．４２ｎｍ以下の炭素材料をいう。非黒鉛質炭素の結晶子サイズＬｃは、通常、０．８０～２．０ｎｍである。非黒鉛質炭素としては、難黒鉛化性炭素や、易黒鉛化性炭素が挙げられる。非黒鉛質炭素としては、例えば、樹脂由来の材料、石油ピッチ由来の材料、アルコール由来の材料等が挙げられる。 "Non-graphitic carbon" refers to a carbon material whose average lattice spacing (d 002 ) of the (002) plane is 0.34 nm or more and 0.42 nm or less, as determined by X-ray diffraction before charging and discharging or in a discharge state. say. The crystallite size Lc of non-graphitic carbon is usually 0.80 to 2.0 nm. Examples of non-graphitic carbon include non-graphitizable carbon and easily graphitizable carbon. Examples of non-graphitic carbon include resin-derived materials, petroleum pitch-derived materials, alcohol-derived materials, and the like.
ここで、「放電状態」とは、炭素材料から成る負極活物質を含む負極を作用極として、金属Ｌｉを対極として用いた単極電池において、開回路電圧が０．７Ｖ以上である状態をいう。開回路状態での金属Ｌｉ対極の電位は、Ｌｉの酸化還元電位とほぼ等しいため、上記単極電池における開回路電圧は、Ｌｉの酸化還元電位に対する炭素材料を含む負極の電位とほぼ同等である。つまり、上記単極電池における開回路電圧が０．７Ｖ以上であることは、炭素材料から成る負極活物質から、充放電に伴い吸蔵放出可能なリチウムイオンが十分に放出されていることを意味する。 Here, the "discharge state" refers to a state in which the open circuit voltage is 0.7 V or more in a monopolar battery using a negative electrode containing a negative electrode active material made of carbon material as a working electrode and metal Li as a counter electrode. . Since the potential of the metal Li counter electrode in an open circuit state is approximately equal to the redox potential of Li, the open circuit voltage in the monopolar battery is approximately equal to the potential of the negative electrode containing the carbon material relative to the redox potential of Li. . In other words, if the open circuit voltage of the monopolar battery is 0.7 V or more, it means that a sufficient amount of lithium ions, which can be intercalated and released during charging and discharging, is released from the negative electrode active material made of carbon material. .
「難黒鉛化性炭素」とは、上記ｄ００２が０．３６ｎｍ以上０．４２ｎｍ以下の炭素材料をいう。難黒鉛化性炭素は、通常、非黒鉛質炭素の中でも、３次元的な積層規則性を持つ黒鉛構造が生成し難い性質を有する。 "Non-graphitizable carbon" refers to a carbon material in which the above d 002 is 0.36 nm or more and 0.42 nm or less. Non-graphitizable carbon usually has a property that, even among non-graphitic carbons, it is difficult to form a graphite structure with three-dimensional lamination regularity.
「易黒鉛化性炭素」とは、上記ｄ００２が０．３４ｎｍ以上０．３６ｎｍ未満の炭素材料をいう。易黒鉛化性炭素は、通常、非黒鉛質炭素の中でも、３次元的な積層規則性を持つ黒鉛構造が生成し易い性質を有する。 "Graphitizable carbon" refers to a carbon material in which the above d 002 is 0.34 nm or more and less than 0.36 nm. Graphitizable carbon usually has a property that, among non-graphitic carbons, a graphite structure with three-dimensional lamination regularity is easily generated.
負極合剤における炭素材料から成る負極活物質の含有量の下限としては、１質量％が好ましく、３質量％がより好ましく、５質量％がさらに好ましい。一方、炭素材料から成る負極活物質の含有量の上限としては、５０質量％が好ましく、４０質量％がより好ましく、３０質量％がさらに好ましい。なお、ここで言う「炭素材料から成る負極活物質」とは、炭素材料であって、充放電に伴いリチウムイオンを吸蔵放出する材料のことを意味する。したがって、炭素材料から成る負極活物質は、後述する導電剤やフィラーとしての機能を有してもよい。 The lower limit of the content of the negative electrode active material made of carbon material in the negative electrode mixture is preferably 1% by mass, more preferably 3% by mass, and even more preferably 5% by mass. On the other hand, the upper limit of the content of the negative electrode active material made of carbon material is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. Note that the term "negative electrode active material made of a carbon material" as used herein refers to a carbon material that absorbs and releases lithium ions during charging and discharging. Therefore, the negative electrode active material made of a carbon material may function as a conductive agent or filler, which will be described later.
負極合剤における負極活物質の含有量の下限としては、１０質量％が好ましく、１５質量％がより好ましい。一方、負極活物質の含有量の上限としては、６０質量％が好ましく、７０質量％がより好ましく、８０質量％がさらに好ましく、９０質量％がよりさらに好ましく、９５質量％であってもよい。負極活物質の含有量を前記範囲とすることで、当該アルカリ金属イオン電池の電気容量を高めることができる。 The lower limit of the content of the negative electrode active material in the negative electrode mixture is preferably 10% by mass, more preferably 15% by mass. On the other hand, the upper limit of the content of the negative electrode active material is preferably 60% by mass, more preferably 70% by mass, even more preferably 80% by mass, even more preferably 90% by mass, and may be 95% by mass. By setting the content of the negative electrode active material within the above range, the electric capacity of the alkali metal ion battery can be increased.
（その他の任意の成分）
上記導電剤としては、電池性能に悪影響を与えない導電性材料であれば特に限定されない。このような導電剤としては、天然又は人造の黒鉛、ファーネスブラック、アセチレンブラック、ケッチェンブラック等のカーボンブラック、金属、導電性セラミックスなどが挙げられる。導電剤の形状としては、粉状、繊維状等が挙げられる。上記負極活物質層における導電剤の含有量としては、例えば０．５質量％以上３０質量％以下とすることができる。なお、上述した導電剤のうち、充放電に伴ってリチウムイオンを吸蔵放出する材料は、負極活物質としても作用する。
(Other optional ingredients)
The conductive agent is not particularly limited as long as it is a conductive material that does not adversely affect battery performance. Examples of such conductive agents include natural or artificial graphite, carbon black such as furnace black, acetylene black, and Ketjen black, metals, and conductive ceramics. Examples of the shape of the conductive agent include powder, fiber, and the like. The content of the conductive agent in the negative electrode active material layer can be, for example, 0.5% by mass or more and 30% by mass or less. Note that among the above-mentioned conductive agents, the material that intercalates and releases lithium ions during charging and discharging also acts as a negative electrode active material.
上記バインダー（結着剤）としては、フッ素樹脂（ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等）、ポリエチレン、ポリプロピレン、ポリイミド、ポリアクリル酸等の熱可塑性樹脂；エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のエラストマー；多糖類高分子などが挙げられる。 The above-mentioned binders include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyimide, polyacrylic acid, etc.; ethylene-propylene-diene rubber; (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, and other elastomers; polysaccharide polymers, and the like.
上記フィラーとしては、電池性能に悪影響を与えないものであれば特に限定されない。フィラーの主成分としては、ポリプロピレン、ポリエチレン等のポリオレフィン、シリカ、アルミナ、ゼオライト、ガラス、炭素などが挙げられる。なお、上述したフィラーのうち、充放電に伴ってリチウムイオンを吸蔵放出する材料は、負極活物質としても作用する。 The filler is not particularly limited as long as it does not adversely affect battery performance. Main components of the filler include polyolefins such as polypropylene and polyethylene, silica, alumina, zeolite, glass, and carbon. Note that among the fillers described above, the material that intercalates and releases lithium ions during charging and discharging also acts as a negative electrode active material.
負極合剤層５の平均厚さの下限としては、３０μｍが好ましく、６０μｍがより好ましい。一方、負極合剤層５の平均厚さの上限としては、１０００μｍが好ましく、５００μｍがより好ましく、２００μｍがさらに好ましい。負極合剤層５の平均厚さが上記下限以上とすることで、高いエネルギー密度を有するアルカリ金属イオン電池を得ることができる。一方、負極合剤層５の平均厚さを上記上限以下とすることで、高率放電性能に優れ、活物質利用率の高い負極を備えるアルカリ金属イオン電池を得ることができる。 The lower limit of the average thickness of the negative electrode mixture layer 5 is preferably 30 μm, more preferably 60 μm. On the other hand, the upper limit of the average thickness of the negative electrode mixture layer 5 is preferably 1000 μm, more preferably 500 μm, and even more preferably 200 μm. By setting the average thickness of the negative electrode mixture layer 5 to be equal to or greater than the above lower limit, an alkali metal ion battery having high energy density can be obtained. On the other hand, by setting the average thickness of the negative electrode mixture layer 5 to be equal to or less than the above upper limit, an alkali metal ion battery having a negative electrode with excellent high rate discharge performance and high active material utilization can be obtained.
上記負極が、表面上にＭｇＳを含有する被膜を備えることが好ましい。上記被膜は、硫化物固体電解質中の硫黄と負極に含まれるマグネシウムとの反応によるものである。金属マグネシウムは、還元力が強いことから負極と硫化物固体電解質との界面にＭｇＳが形成されやすいと推察される。このＭｇＳは、他の固体電解質との界面に形成されるＭｇＯ等と比較してバンドギャップが狭く、電気伝導度に優れていると考えられることから、界面抵抗の上昇が抑制され、金属マグネシウムの絶縁化が軽減されて放電容量及び充放電効率をより高めることができると推察される。 It is preferable that the negative electrode has a coating containing MgS on its surface. The above film is formed by a reaction between sulfur in the sulfide solid electrolyte and magnesium contained in the negative electrode. Since metallic magnesium has a strong reducing power, it is presumed that MgS is likely to be formed at the interface between the negative electrode and the sulfide solid electrolyte. This MgS has a narrower bandgap and is thought to have superior electrical conductivity compared to MgO, etc., which is formed at the interface with other solid electrolytes, so it suppresses the increase in interfacial resistance and makes the metal magnesium It is inferred that insulation is reduced and discharge capacity and charge/discharge efficiency can be further enhanced.
［中間層］
上記中間層は、負極基材の表面の被覆層であり、炭素粒子等の導電性粒子を含むことで負極基材と負極活物質層との接触抵抗を低減する。中間層の構成は特に限定されず、例えば樹脂バインダー及び導電性粒子を含有する組成物により形成できる。
[Middle layer]
The intermediate layer is a coating layer on the surface of the negative electrode base material, and contains conductive particles such as carbon particles to reduce contact resistance between the negative electrode base material and the negative electrode active material layer. The structure of the intermediate layer is not particularly limited, and can be formed, for example, from a composition containing a resin binder and conductive particles.
＜正極層＞
正極層２は、正極基材層７と、この正極基材層７の表面に積層される正極合剤層６とを備える。また、正極層２は、負極層１と同様、正極基材層７と正極合剤層６との間に中間層を有していてもよい。この中間層は負極層１の中間層と同様の構成とすることができる。
<Positive electrode layer>
The positive electrode layer 2 includes a positive electrode base material layer 7 and a positive electrode mixture layer 6 laminated on the surface of the positive electrode base material layer 7. Further, like the negative electrode layer 1, the positive electrode layer 2 may have an intermediate layer between the positive electrode base material layer 7 and the positive electrode mixture layer 6. This intermediate layer can have the same structure as the intermediate layer of the negative electrode layer 1.
［正極基材層］
正極基材層７は、負極基材層４と同様の構成とすることができる。正極基材層７の材質としては、導電体であればどのようなものでもよく、例えば、銅、アルミニウム、チタン、ニッケル、タンタル、ニオブ、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモン、金、銀、鉄、白金、クロム、スズ、インジウム及びこれらの一種以上を含む合金並びにステンレス合金からなる群から選択される一種以上の金属を挙げることができる。
[Positive electrode base material layer]
The positive electrode base material layer 7 can have the same structure as the negative electrode base material layer 4. The material of the positive electrode base layer 7 may be any conductor, such as copper, aluminum, titanium, nickel, tantalum, niobium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, gold, Examples include one or more metals selected from the group consisting of silver, iron, platinum, chromium, tin, indium, alloys containing one or more of these, and stainless steel alloys.
正極基材層７の平均厚さの下限としては、３μｍが好ましく、５μｍがより好ましい。一方、正極基材層７の平均厚さの上限としては、２００μｍが好ましく、１００μｍがより好ましく、５０μｍがさらに好ましい。正極基材層７の平均厚さが上記下限以上とすることで、正極基材層７の強度を十分に高くできるため、正極層２を良好に形成できる。一方、正極基材層７の平均厚さを上記上限以下とすることで、他の構成要素の体積を十分に確保できる。 The lower limit of the average thickness of the positive electrode base material layer 7 is preferably 3 μm, more preferably 5 μm. On the other hand, the upper limit of the average thickness of the positive electrode base material layer 7 is preferably 200 μm, more preferably 100 μm, and even more preferably 50 μm. By making the average thickness of the positive electrode base material layer 7 equal to or more than the above lower limit, the strength of the positive electrode base material layer 7 can be sufficiently increased, so that the positive electrode layer 2 can be formed satisfactorily. On the other hand, by setting the average thickness of the positive electrode base material layer 7 to be equal to or less than the above upper limit, a sufficient volume of other components can be ensured.
［正極合剤層］
正極合剤層６は、正極活物質を含むいわゆる正極合剤から形成することができる。また、正極合剤層６を形成する正極合剤は、負極合剤と同様、必要に応じて導電剤、バインダー、フィラー等の任意成分を含む。
[Positive electrode mixture layer]
The positive electrode mixture layer 6 can be formed from a so-called positive electrode mixture containing a positive electrode active material. Further, the positive electrode mixture forming the positive electrode mixture layer 6 contains optional components such as a conductive agent, a binder, and a filler as necessary, like the negative electrode mixture.
正極合剤層６に含まれる正極活物質としては、アルカリ金属イオン電池に通常用いられる公知のものが使用できる。上記正極活物質としては、例えばＬｉｘＭＯｙ（Ｍは少なくとも一種の遷移金属を表す）で表される複合酸化物（層状のα－ＮａＦｅＯ２型結晶構造を有するＬｉｘＣｏＯ２，ＬｉｘＮｉＯ２，ＬｉｘＭｎＯ３，ＬｉｘＮｉαＣｏ（１－α）Ｏ２，ＬｉｘＮｉαＭｎβＣｏ（１－α－β）Ｏ２等、スピネル型結晶構造を有するＬｉｘＭｎ２Ｏ４，ＬｉｘＮｉαＭｎ（２－α）Ｏ４等）、ＬｉｗＭｅｘ（ＡＯｙ）ｚ（Ｍｅは少なくとも一種の遷移金属を表し、Ａは例えばＰ、Ｓｉ、Ｂ、Ｖ等を表す）で表されるポリアニオン化合物（ＬｉＦｅＰＯ４，ＬｉＭｎＰＯ４，ＬｉＮｉＰＯ４，ＬｉＣｏＰＯ４，Ｌｉ３Ｖ２（ＰＯ４）３，Ｌｉ２ＭｎＳｉＯ４，Ｌｉ２ＣｏＰＯ４Ｆ等）が挙げられる。これらの化合物中の元素又はポリアニオンは、他の元素又はアニオン種で一部が置換されていてもよい。また、正極活物質としては、Ｌｉ－Ａｌ、Ｌｉ－Ｉｎ、Ｌｉ－Ｓｎ、Ｌｉ－Ｐｂ、Ｌｉ－Ｂｉ、Ｌｉ－Ｇａ、Ｌｉ－Ｓｒ、Ｌｉ－Ｓｉ、Ｌｉ－Ｚｎ、Ｌｉ－Ｃｄ、Ｌｉ－Ｃａ、Ｌｉ－Ｂａ等のリチウム合金、ＮａＣｒＯ２、ＮａＮｉ１／２Ｍｎ１／２Ｏ２等のナトリウム遷移金属酸化物、ＫＣｏＯ２等のカリウム遷移金属酸化物、ＫＶＰＯ４、ＫＶＯＰＯ４等のポリアニオン化合物などの反応電位が負極活物質よりも貴な材料を用いることができる。正極活物質層においては、これら化合物の１種を単独で用いてもよく、２種以上を混合して用いてもよい。 As the positive electrode active material contained in the positive electrode mixture layer 6, known materials commonly used in alkali metal ion batteries can be used. Examples of the positive electrode active material include complex oxides represented by Li x MO y (M represents at least one type of transition metal) (Li x CoO 2 having a layered α-NaFeO 2 type crystal structure, Li x NiO 2 , Li x MnO 3 , Li x Ni α Co (1-α) O 2 , Li x Ni α Mn β Co (1-α-β) O 2 , etc., which have a spinel type crystal structure . , Li x Ni α Mn (2-α) O 4 , etc.), Li w Me x (AO y ) z (Me represents at least one type of transition metal, and A represents, for example, P, Si, B, V, etc.) Examples include polyanion compounds represented by (LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , Li 2 CoPO 4 F, etc.). The elements or polyanions in these compounds may be partially substituted with other elements or anion species. In addition, as positive electrode active materials, Li-Al, Li-In, Li-Sn, Li-Pb, Li-Bi, Li-Ga, Li-Sr, Li-Si, Li-Zn, Li-Cd, Li- Lithium alloys such as Ca, Li-Ba, sodium transition metal oxides such as NaCrO 2 , NaNi 1/2 Mn 1/2 O 2 , potassium transition metal oxides such as KCoO 2 , polyanionic compounds such as KVPO 4 and KVOPO 4 A material whose reaction potential is nobler than that of the negative electrode active material can be used. In the positive electrode active material layer, one type of these compounds may be used alone, or two or more types may be used in combination.
正極合剤層６の平均厚さの下限としては、３０μｍが好ましく、６０μｍがより好ましい。一方、正極合剤層６の平均厚さの上限としては、１０００μｍが好ましく、５００μｍがより好ましく、２００μｍがさらに好ましい。正極合剤層６の平均厚さが上記下限以上とすることで、高いエネルギー密度を有するアルカリ金属イオン電池を得ることができる。一方、正極合剤層６の平均厚さを上記上限以下とすることで、高率放電性能に優れ、活物質利用率の高い負極を備えるアルカリ金属イオン電池を得ることができる。 The lower limit of the average thickness of the positive electrode mixture layer 6 is preferably 30 μm, more preferably 60 μm. On the other hand, the upper limit of the average thickness of the positive electrode mixture layer 6 is preferably 1000 μm, more preferably 500 μm, and even more preferably 200 μm. By setting the average thickness of the positive electrode mixture layer 6 to be equal to or greater than the above lower limit, an alkali metal ion battery having high energy density can be obtained. On the other hand, by setting the average thickness of the positive electrode mixture layer 6 to be equal to or less than the above upper limit, an alkali metal ion battery having a negative electrode with excellent high rate discharge performance and high active material utilization can be obtained.
＜固体電解質層＞
固体電解質層３は、硫化物固体電解質を含有する。固体電解質層３が硫化物固体電解質を含有することで、イオン伝導度が良好であり、界面形成が容易である。硫化物固体電解質は、非晶質、ガラス、結晶等の構造を有する。また、硫化物固体電解質に、Ｌｉ３ＰＯ４やハロゲン、ハロゲン化合物等を添加してもよい。
<Solid electrolyte layer>
Solid electrolyte layer 3 contains a sulfide solid electrolyte. Since the solid electrolyte layer 3 contains the sulfide solid electrolyte, it has good ionic conductivity and can easily form an interface. Sulfide solid electrolytes have structures such as amorphous, glass, and crystal. Furthermore, Li 3 PO 4 , halogen, halogen compounds, etc. may be added to the sulfide solid electrolyte.
硫化物固体電解質としては、Ｌｉイオン伝導性が高いことが好ましく、例えばＬｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＩ、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＣｌ、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＬｉＢｒ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ２Ｏ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ２Ｏ－ＬｉＩ、Ｌｉ２Ｓ－Ｐ２Ｓ５－Ｌｉ３Ｎ、Ｌｉ２Ｓ－ＳｉＳ２、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＩ、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＢｒ、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉＣｌ、Ｌｉ２Ｓ－ＳｉＳ２－Ｂ２Ｓ３－ＬｉＩ、Ｌｉ２Ｓ－ＳｉＳ２－Ｐ２Ｓ５－ＬｉＩ、Ｌｉ２Ｓ－Ｂ２Ｓ３、Ｌｉ２Ｓ－Ｐ２Ｓ５－ＺｍＳ２ｎ（ただし、ｍ、ｎは正の数、Ｚは、Ｇｅ、Ｚｎ、Ｇａのいずれかである。）、Ｌｉ２Ｓ－ＧｅＳ２、Ｌｉ２Ｓ－ＳｉＳ２－Ｌｉ３ＰＯ４、Ｌｉ２Ｓ－ＳｉＳ２－ＬｉｘＭＯｙ（ただし、ｘ、ｙは正の数、Ｍは、Ｐ、Ｓｉ、Ｇｅ、Ｂ、Ａｌ、Ｇａ、Ｉｎのいずれかである。）、Ｌｉ１０ＧｅＰ２Ｓ１２等を挙げることができる。これらの中でも、リチウムイオン伝導性が良好な観点から、Ｌｉ２Ｓ－Ｐ２Ｓ５が好ましく、ｘＬｉ２Ｓ－（１００－ｘ）Ｐ２Ｓ５（７０≦ｘ≦８０）が好ましい。 The sulfide solid electrolyte preferably has high Li ion conductivity, such as Li 2 SP 2 S 5 , Li 2 SP 2 S 5 -LiI, Li 2 SP 2 S 5 -LiCl, Li 2 S-P 2 S 5 -LiBr, Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-P 2 S 5 -Li 3 N , Li 2 S-SiS 2 , Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -LiBr, Li 2 S-SiS 2 -LiCl, Li 2 S-SiS 2 -B 2 S 3 -LiI, Li 2 S-SiS 2 -P 2 S 5 -LiI, Li 2 S-B 2 S 3 , Li 2 S-P 2 S 5 -Z m S 2n (m and n are positive numbers, Z is Ge , Zn, Ga), Li 2 S-GeS 2 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 2 S-SiS 2 -Li x MO y (However, x and y are positive The number M is any one of P, Si, Ge, B, Al, Ga, and In.), Li 10 GeP 2 S 12 , and the like. Among these, from the viewpoint of good lithium ion conductivity, Li 2 SP 2 S 5 is preferred, and xLi 2 S-(100-x)P 2 S 5 (70≦x≦80) is preferable.
硫化物固体電解質の電気伝導度としては１×１０－９Ω・ｃｍ以下が好ましい。固体電解質の体積抵抗率が上記範囲であることで、固体電解質層３の機能として必要な絶縁性を担保できる。上記硫化物固体電解質の電気伝導度は、ＪＩＳ－Ｋ－０１３０（２００８年）に準拠して測定される。 The electrical conductivity of the sulfide solid electrolyte is preferably 1×10 −9 Ω·cm or less. When the volume resistivity of the solid electrolyte is within the above range, the insulation required as a function of the solid electrolyte layer 3 can be ensured. The electrical conductivity of the sulfide solid electrolyte is measured in accordance with JIS-K-0130 (2008).
負極合剤における負極活物質と固体電解質との含有割合としては、例えば質量比で負極活物質：固体電解質＝９５：５～１０：９０の範囲内であることが好ましく、９０：１０～１５：８５の範囲内であることがより好ましい。負極活物質と固体電解質との含有割合が上記範囲であることで、良好なイオン伝導性が確保できる。 The content ratio of the negative electrode active material and solid electrolyte in the negative electrode mixture is preferably within the range of negative electrode active material: solid electrolyte = 95:5 to 10:90 in mass ratio, for example, 90:10 to 15: More preferably, it is within the range of 85. When the content ratio of the negative electrode active material and solid electrolyte is within the above range, good ionic conductivity can be ensured.
固体電解質層３の平均厚さの下限としては、１μｍが好ましく、３μｍがより好ましい。一方、固体電解質層３の平均厚さの上限としては、５０μｍが好ましく、２０μｍがより好ましい。固体電解質層３の平均厚さが上記下限以上とすることで、正極と負極とを確実に絶縁することが可能となる。一方、固体電解質層３の平均厚さを上記上限以下とすることで、アルカリ金属イオン電池のエネルギー密度を高めることが可能となる。 The lower limit of the average thickness of the solid electrolyte layer 3 is preferably 1 μm, more preferably 3 μm. On the other hand, the upper limit of the average thickness of the solid electrolyte layer 3 is preferably 50 μm, more preferably 20 μm. By setting the average thickness of the solid electrolyte layer 3 to be at least the above lower limit, it becomes possible to reliably insulate the positive electrode and the negative electrode. On the other hand, by making the average thickness of the solid electrolyte layer 3 below the above upper limit, it becomes possible to increase the energy density of the alkali metal ion battery.
＜アルカリ金属イオン電池の製造方法＞
当該アルカリ金属イオン電池の製造方法は、負極合剤作製工程と、固体電解質作製工程と、正極合剤作製工程と、負極層、固体電解質層及び正極層を積層する積層工程とを主に備える。
<Method for manufacturing an alkali metal ion battery>
The method for manufacturing the alkali metal ion battery mainly includes a negative electrode mixture manufacturing process, a solid electrolyte manufacturing process, a positive electrode mixture manufacturing process, and a lamination process of laminating a negative electrode layer, a solid electrolyte layer, and a positive electrode layer.
［負極合剤作製工程］
本工程では、負極層を形成するための負極合剤が作製される。負極合剤の作製方法としては、特に制限はなく、例えばメカニカルミリング法等を用いて負極活物質を作製することを備える。
[Negative electrode mixture production process]
In this step, a negative electrode mixture for forming a negative electrode layer is prepared. The method for producing the negative electrode mixture is not particularly limited, and includes, for example, producing the negative electrode active material using a mechanical milling method or the like.
［固体電解質作製工程］
本工程では、固体電解質層を形成するための上記固体電解質が作製される。本工程では、固体電解質の所定の材料をメカニカルミリング法により処理して得ることができる。また、溶融急冷法により固体電解質の所定の材料を溶融温度以上に加熱して所定の比率で両者を溶融混合し、急冷することにより固体電解質を作製してもよい。さらに、その他の固体電解質の合成方法としては、例えば真空封入して焼成する固相法、溶解析出などの液相法、気相法（ＰＬＤ）、メカニカルミリング後にアルゴン雰囲気下で焼成することなどが挙げられる。
[Solid electrolyte production process]
In this step, the solid electrolyte for forming the solid electrolyte layer is produced. In this step, the solid electrolyte can be obtained by processing a predetermined material using a mechanical milling method. Alternatively, the solid electrolyte may be prepared by heating a predetermined material of the solid electrolyte to a temperature higher than the melting temperature by a melt quenching method, melting and mixing the materials at a predetermined ratio, and rapidly cooling the materials. Furthermore, other methods for synthesizing solid electrolytes include, for example, a solid phase method using vacuum sealing and firing, a liquid phase method such as solution deposition, a gas phase method (PLD), and firing under an argon atmosphere after mechanical milling. Can be mentioned.
［正極合剤作製工程］
本工程では、正極層を形成するための正極合剤が作製される。正極合剤の作製方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、正極活物質の圧縮成形、正極合剤の所定の材料のメカニカルミリング処理、正極活物質のターゲット材料を用いたスパッタリング等が挙げられる。
[Positive electrode mixture production process]
In this step, a positive electrode mixture for forming a positive electrode layer is prepared. The method for producing the positive electrode mixture is not particularly limited and can be selected as appropriate depending on the purpose. For example, compression molding of the positive electrode active material, mechanical milling treatment of a predetermined material of the positive electrode mixture, Examples include sputtering using a target material.
［積層工程］
本工程は、負極層、固体電解質層及び正極層が積層される。本工程では、負極層、固体電解質層、及び正極層を順次形成してもよいし、この逆であってもよく、各層の形成の順序は特に問わない。
[Lamination process]
In this step, a negative electrode layer, a solid electrolyte layer, and a positive electrode layer are laminated. In this step, the negative electrode layer, the solid electrolyte layer, and the positive electrode layer may be formed in this order, or the reverse may be performed, and the order of formation of each layer is not particularly limited.
また、負極合剤、固体電解質及び正極合剤を一度に加圧成型することにより、負極層、固体電解質層及び正極層が積層されてもよい。また、正極層、負極層、又はこれらの層を予め成形し、固体電解質層と加圧成型して積層してもよい。 Alternatively, the negative electrode layer, the solid electrolyte layer, and the positive electrode layer may be laminated by pressure-molding the negative electrode mixture, solid electrolyte, and positive electrode mixture at once. Alternatively, the positive electrode layer, the negative electrode layer, or these layers may be formed in advance and laminated by pressure molding with the solid electrolyte layer.
［その他の実施形態］
本発明は上記実施形態に限定されるものではなく、上記態様の他、種々の変更、改良を施した態様で実施することができる。
[Other embodiments]
The present invention is not limited to the embodiments described above, and can be implemented in various modifications and improvements in addition to the embodiments described above.
本発明に係るアルカリ金属イオン電池の構成については特に限定されるものではなく、例えば中間層や接着層のように、負極層、正極層及び固体電解質層以外のその他の層を備えていてもよい。 The structure of the alkali metal ion battery according to the present invention is not particularly limited, and may include layers other than the negative electrode layer, positive electrode layer, and solid electrolyte layer, such as an intermediate layer or an adhesive layer. .
＜実施例＞
以下、実施例によって本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
<Example>
EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［実施例１］
（アルカリ金属イオン電池セルの作製）
以下の工程に従い、アルカリ金属イオン電池セルを作製した。なお、以下の工程は、不活性雰囲気下（Ａｒ）で実施した。
（１）錠剤成型器と同じ内径（１０ｍｍφ）のカーボンペーパー（基材層）を錠剤成型器の底部に配置した。
（２）カーボンペーパーに金属マグネシウム粒子（平均粒径１６０μｍ）と、７５Ｌｉ２Ｓ－２５Ｐ２Ｓ５粉末とを質量比で７０：３０となるよう混合した後、充填して加圧することにより、負極合剤層を形成した。
（３）その上から所定の質量比の７５Ｌｉ２Ｓ－２５Ｐ２Ｓ５粉末を添加して加圧することにより、固体電解質層を形成した。
（４）カーボンペーパーと金属マグネシウム粒子と７５Ｌｉ２Ｓ－２５Ｐ２Ｓ５粉末とからなるペレットを錠剤形成器から取り出さないまま、その上から１０ｍｍφのＩｎ、９ｍｍφのＬｉの順に金属箔をのせ、加圧してアルカリ金属イオン電池セルを作製した。
[Example 1]
(Preparation of alkali metal ion battery cell)
An alkali metal ion battery cell was produced according to the following steps. Note that the following steps were performed under an inert atmosphere (Ar).
(1) Carbon paper (base material layer) having the same inner diameter (10 mmφ) as the tablet molding machine was placed at the bottom of the tablet molding machine.
(2) After mixing metal magnesium particles (average particle size 160 μm) and 75Li 2 S-25P 2 S 5 powder in a mass ratio of 70:30 in carbon paper, the mixture is filled and pressurized to form a negative electrode. A mixture layer was formed.
(3) A solid electrolyte layer was formed by adding 75Li 2 S-25P 2 S 5 powder at a predetermined mass ratio thereon and applying pressure.
(4) Without taking out the pellet consisting of carbon paper, metal magnesium particles, and 75Li 2 S-25P 2 S 5 powder from the tablet forming machine, metal foil was placed on top of it in the order of 10 mmφ In and 9 mmφ Li, and the pellet was processed. An alkali metal ion battery cell was produced by pressing.
［実施例２及び実施例３］
（アルカリ金属イオン電池セルの作製）
次の点を変更したこと以外は、実施例１と同様の操作をして、実施例２及び実施例３のアルカリ金属イオン電池セルを作製した。実施例２の負極合剤として金属マグネシウム粒子（平均粒径１０μｍ）と７５Ｌｉ２Ｓ－２５Ｐ２Ｓ５粉末とを質量比で４０：６０の割合で含有させた。また、実施例３の負極合剤として金属マグネシウム粒子（平均粒径１０μｍ）と黒鉛粉末と７５Ｌｉ２Ｓ－２５Ｐ２Ｓ５粉末とを質量比で４０：１０：５０の割合で含有させた。対極として１０ｍｍφの金属Ｌｉを用い、実施例２及び実施例３のアルカリ金属イオン電池セルを作製した。
[Example 2 and Example 3]
(Preparation of alkali metal ion battery cell)
Alkali metal ion battery cells of Example 2 and Example 3 were produced in the same manner as in Example 1 except for the following changes. The negative electrode mixture of Example 2 contained magnesium metal particles (average particle size 10 μm) and 75Li 2 S-25P 2 S 5 powder in a mass ratio of 40:60. Further, as the negative electrode mixture of Example 3, metallic magnesium particles (average particle size 10 μm), graphite powder, and 75Li 2 S-25P 2 S 5 powder were contained in a mass ratio of 40:10:50. Alkali metal ion battery cells of Example 2 and Example 3 were produced using metal Li having a diameter of 10 mm as a counter electrode.
［比較例１及び比較例２］
（アルカリ金属イオン電池セルの作製）
次の点を変更したこと以外は、実施例１と同様の操作をして、比較例１及び比較例２のアルカリ金属イオン電池セルを作製した。基材層としてＮｉメッシュ、負極合剤として金属マグネシウム粒子とポリアクリル酸バインダーとを質量比で８０：２０の割合で含有させたものを用い、１２ｍｍφの合剤負極を作製した。電解質としては、ＥＣ及びＤＭＣを１：２の体積比で混合した溶媒にＬｉＴＦＳＩを１ｍｏｌ／ｄｍ３の濃度で溶解させて比較例１の非水電解質とした。また、ＥＣ及びＤＭＣを１：２の体積比で混合した溶媒にヘキサフルオロリン酸リチウム（ＬｉＰＦ６）を１ｍｏｌ／ｄｍ３の濃度で溶解させて比較例２の非水電解質とした。そして、対極として１６ｍｍφの金属Ｌｉを用い、比較例１及び比較例２のアルカリ金属イオン電池セルを作製した。
[Comparative Example 1 and Comparative Example 2]
(Preparation of alkali metal ion battery cell)
Alkali metal ion battery cells of Comparative Example 1 and Comparative Example 2 were produced in the same manner as in Example 1 except for the following changes. A mixture negative electrode of 12 mm diameter was prepared using a Ni mesh as the base material layer and a negative electrode mixture containing metal magnesium particles and a polyacrylic acid binder in a mass ratio of 80:20. As the electrolyte, a nonaqueous electrolyte of Comparative Example 1 was prepared by dissolving LiTFSI at a concentration of 1 mol/dm 3 in a solvent in which EC and DMC were mixed at a volume ratio of 1:2. In addition, lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 1 mol/dm 3 in a solvent in which EC and DMC were mixed at a volume ratio of 1:2 to obtain a nonaqueous electrolyte of Comparative Example 2. Then, alkali metal ion battery cells of Comparative Example 1 and Comparative Example 2 were produced using metal Li having a diameter of 16 mm as a counter electrode.
（充電状態の負極のＸＲＤパターンの測定）
電解質として固体電解質を用いた実施例１における負極の充放電反応が金属マグネシウムとＬｉ＋イオンとの反応によるものであるのかを確認するために、充電状態の負極のＸＲＤパターンの測定を行った。なお、ＸＲＤパターンの測定にあたっては、セル解体による負極の取り出しからＸＲＤ測定器による測定までの工程はＡｒ雰囲気下で実施した。
(Measurement of XRD pattern of negative electrode in charged state)
In order to confirm whether the charge/discharge reaction of the negative electrode in Example 1 using a solid electrolyte as the electrolyte is due to the reaction between metal magnesium and Li + ions, the XRD pattern of the negative electrode in the charged state was measured. Note that in measuring the XRD pattern, the steps from taking out the negative electrode by disassembling the cell to measurement using an XRD measuring device were performed in an Ar atmosphere.
図２は、実施例１の負極のＸ線回折（ＸＲＤ）スペクトルである。図２（ａ）は、２θ＝１０°～９０°の範囲におけるＸＲＤスペクトルを示し、図２（ｂ）は、図２（ａ）をさらに拡大して２θ＝５０°～７０°の範囲におけるＸＲＤスペクトルを示す。図２に示されるように、実施例１の充電状態の負極のＸＲＤパターンにおける５２°及び６５°近傍にみられるピークの位置は、Ｌｉ０．３６Ｍｇ０．６４合金のＸＲＤパターンにおけるピークの位置と一致していた。このことから、実施例１の充電後にＬｉＸＭｇＹ合金が形成されたことがわかる。従って、固体電解質を用いることで、金属マグネシウムとＬｉ＋イオンとが良好に反応しており、負極の充放電反応が金属マグネシウムとＬｉ＋イオンとの反応によるものであることが示された。なお、ＸＲＤパターンの測定には、Ｘ線回折装置であるＲＩＮＴ ＰＴＲ３（Ｒｉｇａｋｕ社製）を用い、線源はＣｕＫαとした。 FIG. 2 is an X-ray diffraction (XRD) spectrum of the negative electrode of Example 1. Fig. 2(a) shows the XRD spectrum in the range of 2θ = 10° to 90°, and Fig. 2(b) shows the XRD spectrum in the range of 2θ = 50° to 70° by further expanding Fig. 2(a). The spectrum is shown. As shown in FIG. 2, the positions of the peaks observed near 52° and 65° in the XRD pattern of the charged negative electrode of Example 1 are the same as the positions of the peaks in the XRD pattern of the Li 0.36 Mg 0.64 alloy. It was consistent with This shows that a Li x Mg Y alloy was formed after charging in Example 1. Therefore, by using the solid electrolyte, metal magnesium and Li + ions reacted well, and it was shown that the charge/discharge reaction of the negative electrode was due to the reaction between metal magnesium and Li + ions. Note that for the measurement of the XRD pattern, an X-ray diffractometer, RINT PTR3 (manufactured by Rigaku), was used, and the radiation source was CuKα.
（充放電試験）
上記実施例１のアルカリ金属イオン電池セルについて、５０℃環境下で充放電を実施した。充電は、充電電流０．００２５Ｃ、充電終止電圧－０．６Ｖ（対極Ｌｉ換算で０Ｖ）、総充電時間２０時間の定電流定電圧（ＣＣＣＶ）充電とした。放電は、放電電流０．００２５Ｃ、放電終止電圧０．９Ｖ（対極Ｌｉ換算で１．５Ｖ）の定電流（ＣＣ）放電として１サイクルの初回充放電を行った。充電と放電の間には、３０分の休止を設けた。なお、実施例１の１Ｃは金属マグネシウムの理論容量３３５０ｍＡｈ／ｇを基準とした。ここで、金属マグネシウムにＬｉ＋イオンが吸蔵される還元反応を「充電」、Ｌｉ＋イオンが放出される酸化反応を「放電」という。
上記１サイクル目の放電容量を実施例１の「初回放電容量（ｍＡｈ／ｇ）」とした。
(Charge/discharge test)
The alkali metal ion battery cell of Example 1 was charged and discharged in a 50°C environment. Charging was constant current constant voltage (CCCV) charging at a charging current of 0.0025 C, a charging end voltage of −0.6 V (0 V in terms of counter electrode Li), and a total charging time of 20 hours. Discharge was performed as constant current (CC) discharge with a discharge current of 0.0025 C and a discharge end voltage of 0.9 V (1.5 V in terms of counter electrode Li), and one cycle of initial charging and discharging was performed. A 30 minute break was provided between charging and discharging. Note that 1C in Example 1 was based on the theoretical capacity of metal magnesium of 3350 mAh/g. Here, the reduction reaction in which Li + ions are occluded in metallic magnesium is called "charging," and the oxidation reaction in which Li + ions are released is called "discharging."
The discharge capacity of the first cycle was defined as the "initial discharge capacity (mAh/g)" of Example 1.
次に、比較例１及び比較例２のアルカリ金属イオン電池セルについて、５０℃環境下で充放電を実施した。充電は、充電電流０．００２５Ｃ、充電終止電圧０．０２Ｖ、総充電時間２０時間の定電圧（ＣＣＣＶ）充電とした。放電は、放電電流０．００２５Ｃ、放電終止電圧１．５Ｖの定電流（ＣＣ）放電として１サイクルの初回充放電を行った。充電と放電の間には、３０分の休止を設けた。なお、比較例１及び比較例２のアルカリ金属イオン電池の１Ｃは、実施例１と同様、金属マグネシウムの理論容量３３５０ｍＡｈ／ｇを基準とした。
上記１サイクル目の放電容量を比較例１及び比較例２の「初回放電容量（ｍＡｈ／ｇ）」とした。
Next, the alkali metal ion battery cells of Comparative Example 1 and Comparative Example 2 were charged and discharged in a 50° C. environment. Charging was constant voltage (CCCV) charging with a charging current of 0.0025 C, a charging end voltage of 0.02 V, and a total charging time of 20 hours. For the discharge, one cycle of initial charging and discharging was performed as a constant current (CC) discharge with a discharge current of 0.0025 C and a discharge end voltage of 1.5 V. A 30 minute break was provided between charging and discharging. Note that 1C of the alkali metal ion batteries of Comparative Examples 1 and 2 was based on the theoretical capacity of metal magnesium of 3350 mAh/g, as in Example 1.
The discharge capacity of the first cycle was defined as the "initial discharge capacity (mAh/g)" of Comparative Example 1 and Comparative Example 2.
さらに、実施例２及び実施例３のアルカリ金属イオン電池セルについて、５０℃環境下で充放電を実施した。充電は、充電電流０．００７５Ｃ、充電終止電圧０．０１Ｖで定電流充電を行った後、０．０１Ｖの定電圧で電流密度が０．００３７５Ｃに相当する値に減衰するまで定電圧充電し、放電は、放電電流０．００７５Ｃ、放電終止電圧１．２Ｖの定電流（ＣＣ）放電として１サイクルの初回充放電を行った。充電と放電の間には、３０分の休止を設けた。なお、実施例２及び実施例３のアルカリ金属イオン電池の１Ｃは、実施例１と同様、金属マグネシウムの理論容量３３５０ｍＡｈ／ｇを基準とした。
上記１サイクル目の放電容量を実施例２及び実施例３の「初回放電容量（ｍＡｈ／ｇ）」とした。ここで、「初回放電容量」とは、金属マグネシウムの質量あたりの放電容量を意味する。
Furthermore, the alkali metal ion battery cells of Example 2 and Example 3 were charged and discharged in an environment of 50°C. For charging, after performing constant current charging at a charging current of 0.0075C and a charging end voltage of 0.01V, constant voltage charging was performed at a constant voltage of 0.01V until the current density attenuated to a value corresponding to 0.00375C. For the discharge, one cycle of initial charging and discharging was performed as a constant current (CC) discharge with a discharge current of 0.0075 C and a discharge end voltage of 1.2 V. A 30 minute break was provided between charging and discharging. Note that 1C of the alkali metal ion batteries of Examples 2 and 3 was based on the theoretical capacity of metal magnesium of 3350 mAh/g, as in Example 1.
The discharge capacity at the first cycle was defined as the "initial discharge capacity (mAh/g)" in Examples 2 and 3. Here, the "initial discharge capacity" means the discharge capacity per mass of metal magnesium.
（充放電カーブの特性）
図３は、実施例１及び比較例１～比較例２の充放電サイクル性能カーブを示すグラフである。図３においては、電解質として硫化物固体電解質を用いた場合、液体電解質に比べて、充電カーブにおける１．２Ｖｖｓ．Ｌｉ／Ｌｉ＋以下のショルダーが小さく、放電カーブにおけるＭｇとＬｉ＋イオンとの脱合金化反応に起因する０．２Ｖｖｓ．Ｌｉ／Ｌｉ＋近傍のプラトー領域が長いことが示されている。
(Charge/discharge curve characteristics)
FIG. 3 is a graph showing the charge/discharge cycle performance curves of Example 1 and Comparative Examples 1 and 2. In FIG. 3, when a sulfide solid electrolyte is used as the electrolyte, compared to a liquid electrolyte, the charge curve is 1.2V vs. The shoulder below Li/Li + is small and is 0.2V vs. due to the dealloying reaction between Mg and Li + ions in the discharge curve. It is shown that the plateau region near Li/Li + is long.
（充放電サイクル試験）
（１）充放電サイクル試験
実施例１、及び比較例１～比較例２のアルカリ金属イオン電池を、上記充電、休止及び放電の工程を１サイクルとして、このサイクルを５サイクル繰り返した。充電、放電及び休止ともに、５０℃の恒温槽内で行った。
(Charge/discharge cycle test)
(1) Charge/Discharge Cycle Test The alkali metal ion batteries of Example 1 and Comparative Examples 1 and 2 were subjected to 5 cycles of the above-mentioned charging, resting, and discharging steps, one cycle being repeated. Charging, discharging, and resting were all carried out in a constant temperature bath at 50°C.
（サイクル後の放電容量）
上記充電及び放電の工程について、５サイクル目の放電容量（ｍＡｈ／ｇ）を５サイクル後の放電容量とした。
(discharge capacity after cycle)
Regarding the above charging and discharging steps, the discharge capacity (mAh/g) at the 5th cycle was taken as the discharge capacity after 5 cycles.
（サイクル後の充放電効率）
上記充電及び放電の工程について、５サイクル目の放電容量（ｍＡｈ／ｇ）の充電電気量（Ａｈ）に対する放電容量の百分率を５サイクル後の充放電効率（％）として求め、５サイクル後のクーロン効率とした。
(Charge/discharge efficiency after cycle)
Regarding the above charging and discharging process, the percentage of the discharge capacity (mAh/g) at the 5th cycle with respect to the amount of charged electricity (Ah) is determined as the charging/discharging efficiency (%) after the 5th cycle, and the coulomb after the 5th cycle is determined. Efficiency.
（サイクル後の平均放電電位）
平均放電電位は、放電カーブから面積を求め、横軸の電気量で除した値であり、低いほど負極としての性能が良好である。より具体的には、サイクル後の作用極（負極）の平均放電電位は、図３の放電曲線、直線ｙ＝０、直線ｘ＝（測定された放電容量）に囲まれた領域の面積（単位：ｍＷｈ）を測定された放電容量（単位：ｍＡｈ）で除した値として求めた。
(Average discharge potential after cycling)
The average discharge potential is a value obtained by calculating the area from the discharge curve and dividing it by the amount of electricity on the horizontal axis, and the lower the average discharge potential, the better the performance as a negative electrode. More specifically, the average discharge potential of the working electrode (negative electrode) after cycling is determined by the area (unit: : mWh) divided by the measured discharge capacity (unit: mAh).
また、実施例１及び比較例１～比較例２の初回放電容量、並びに５サイクル後の放電容量、クーロン効率及び平均放電電位を以下の表１に示す。 Further, the initial discharge capacity, discharge capacity after 5 cycles, coulombic efficiency, and average discharge potential of Example 1 and Comparative Examples 1 and 2 are shown in Table 1 below.
表１に示されるように、電解液を使用した場合と比較して、硫化物固体電解質を用いた場合に、高い放電容量、高い充放電効率、及び低い平均放電電位を示す。比較例１～比較例２と比較して、実施例１は５サイクル後の放電容量、充放電効率及び平均放電電位が高く、充放電サイクル性能に優れていた。 As shown in Table 1, the use of the sulfide solid electrolyte exhibits higher discharge capacity, higher charge/discharge efficiency, and lower average discharge potential than when using the electrolyte. Compared to Comparative Examples 1 and 2, Example 1 had higher discharge capacity, charge/discharge efficiency, and average discharge potential after 5 cycles, and was excellent in charge/discharge cycle performance.
また、実施例２及び実施例３の初回放電容量を以下の表２に示す。 Further, the initial discharge capacities of Example 2 and Example 3 are shown in Table 2 below.
表２に示されるように、負極活物質として金属マグネシウムのみを使用した場合と比較して、金属マグネシウムと炭素材料とを併用した場合には、高い放電容量が得られる。
ここで、黒鉛の理論容量を３７２ｍＡｈ／ｇとすると、実施例２に比べて、実施例３における金属マグネシウム粒子の質量あたりの放電容量は、３７２ｍＡｈ／ｇ×０．１（黒鉛粒子の質量％）÷０．４（金属マグネシウム粒子の質量％）＝９３ｍＡｈ／ｇだけ増加することが期待される。しかしながら、実際には１００ｍＡｈ／ｇ以上増加している。このことから、金属Ｍｇと炭素材料とを併用することで、金属マグネシウム粒子の利用率が向上し、放電容量を向上できることが分かる。
As shown in Table 2, a higher discharge capacity can be obtained when metal magnesium and a carbon material are used in combination than when metal magnesium alone is used as the negative electrode active material.
Here, assuming that the theoretical capacity of graphite is 372 mAh/g, compared to Example 2, the discharge capacity per mass of metal magnesium particles in Example 3 is 372 mAh/g x 0.1 (% by mass of graphite particles) An increase of 0.4 (% by mass of metal magnesium particles) = 93 mAh/g is expected. However, in reality, it has increased by more than 100 mAh/g. From this, it can be seen that by using metal Mg and a carbon material together, the utilization rate of metal magnesium particles can be improved and the discharge capacity can be improved.
実施例１に比べ、実施例２は高い放電容量を示す。このような結果が得られた要因としては、負極合剤における硫化物固体電解質の含有割合を高くしたことと、金属マグネシウム粒子の平均粒径を１６０μｍから１０μｍに変更したこととが考えられる。
特に、平均粒径が小さい金属マグネシウム粒子を用いることが、高い放電容量を得るために極めて有効であることが示唆される。
Compared to Example 1, Example 2 shows a higher discharge capacity. The reasons for such results are thought to be that the content of the sulfide solid electrolyte in the negative electrode mixture was increased and the average particle size of the metal magnesium particles was changed from 160 μm to 10 μm.
In particular, it is suggested that using metal magnesium particles with a small average particle size is extremely effective for obtaining high discharge capacity.
以上のように、本発明に係るアルカリ金属イオン電池は、放電容量及び充放電効率が良好であるので、例えばＨＥＶ用のアルカリ金属イオン電池として好適に用いられる。 As described above, since the alkali metal ion battery according to the present invention has good discharge capacity and charge/discharge efficiency, it can be suitably used as an alkali metal ion battery for, for example, an HEV.
１ 負極層
２ 正極層
３ 固体電解質層
４ 負極基材層
５ 負極合剤層
６ 正極合剤層
７ 正極基材層
１０ アルカリ金属イオン電池
1 Negative electrode layer 2 Positive electrode layer 3 Solid electrolyte layer 4 Negative electrode base material layer 5 Negative electrode mixture layer 6 Positive electrode mixture layer 7 Positive electrode base material layer 10 Alkali metal ion battery
Claims (6)
硫化物固体電解質と
を備えるアルカリ金属イオン電池。 a negative electrode having negative electrode active material particles containing magnesium;
An alkali metal ion battery comprising a sulfide solid electrolyte.
硫化物固体電解質と
を備えるアルカリ金属イオン電池（但し、正極と、固体電解質と、負極とを有する全固体電池において、上記負極は、負極部材を備え、上記負極部材は、ステンレスメッシュのの表面にＭｇ層が被覆してなり、放電時に上記負極部材表面においてＬｉのイオン化反応が進行し、充電時に上記負極部材表面においてＬｉの析出反応が進行することを特徴とする全固体電池は除く。）。 a negative electrode containing magnesium;
An alkali metal ion battery comprising a sulfide solid electrolyte (However, in an all-solid battery having a positive electrode, a solid electrolyte, and a negative electrode, the negative electrode is provided with a negative electrode member, and the negative electrode member is attached to the surface of a stainless steel mesh. Excludes all-solid-state batteries which are coated with an Mg layer and are characterized in that an ionization reaction of Li progresses on the surface of the negative electrode member during discharge, and a precipitation reaction of Li progresses on the surface of the negative electrode member during charging.
硫化物固体電解質と
を備え、
上記負極合剤は、マグネシウムを含む負極活物質と、固体電解質とを含有するアルカリ金属イオン電池。 a negative electrode having a negative electrode mixture;
Sulfide solid electrolyte and
Equipped with
The negative electrode mixture is an alkali metal ion battery containing a negative electrode active material containing magnesium and a solid electrolyte.
硫化物固体電解質と
を備え、
上記負極合剤は、マグネシウムを含む負極活物質と、導電剤、バインダー及び／又はフィラーとを含有するアルカリ金属イオン電池。 a negative electrode having a negative electrode mixture;
Sulfide solid electrolyte and
Equipped with
The negative electrode mixture is an alkali metal ion battery containing a negative electrode active material containing magnesium, a conductive agent, a binder, and/ or a filler.
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| JP2014086218A (en) | 2012-10-22 | 2014-05-12 | Toyota Motor Corp | All solid battery system |
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| JP2014086218A (en) | 2012-10-22 | 2014-05-12 | Toyota Motor Corp | All solid battery system |
| JP2016066405A (en) | 2014-09-22 | 2016-04-28 | 公立大学法人大阪府立大学 | Solid electrolyte for all-solid type secondary battery, method for manufacturing the same, and all-solid type secondary battery including the same |
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