JP6711040B2 - リチウム空気電池 - Google Patents
リチウム空気電池 Download PDFInfo
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- JP6711040B2 JP6711040B2 JP2016049175A JP2016049175A JP6711040B2 JP 6711040 B2 JP6711040 B2 JP 6711040B2 JP 2016049175 A JP2016049175 A JP 2016049175A JP 2016049175 A JP2016049175 A JP 2016049175A JP 6711040 B2 JP6711040 B2 JP 6711040B2
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- lithium
- positive electrode
- air battery
- negative electrode
- discharge
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- 229910052744 lithium Inorganic materials 0.000 title claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 63
- 239000008151 electrolyte solution Substances 0.000 claims description 28
- 239000003575 carbonaceous material Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 19
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910018071 Li 2 O 2 Inorganic materials 0.000 description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WUFQNPMBKMKEHN-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F WUFQNPMBKMKEHN-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 150000005678 chain carbonates Chemical class 0.000 description 2
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- 150000005676 cyclic carbonates Chemical class 0.000 description 2
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol 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
- 238000001556 precipitation Methods 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- WVDDUSFOSWWJJH-UHFFFAOYSA-N 1-methyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1 WVDDUSFOSWWJJH-UHFFFAOYSA-N 0.000 description 1
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 1
- 229910007867 Li3.25Ge0.25P0.25S4 Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012047 Li4SiO4-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012075 Li4SiO4-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012057 Li4SiO4—LiI—LiOH 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PCIKPLOQZCYVND-UHFFFAOYSA-N [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C(C)[N+](CCOC)(CC)CC Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C(C)[N+](CCOC)(CC)CC PCIKPLOQZCYVND-UHFFFAOYSA-N 0.000 description 1
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Inert Electrodes (AREA)
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Description
リチウムを吸蔵放出する負極活物質を有する負極と、
結着材を含まない炭素材料からなり、酸素を正極活物質とする正極と、
前記正極に接触しアセトニトリルを含む非水電解液と、
を備えたものである。
カーボンペーパー(東レ製、TGP−H−060)を3.14cm2の面積となるように切り取り、リチウム空気電池の正極とした。このカーボンペーパーは、気体透過性が194(mL・mm/(cm2・h・Pa))であり、直径20μm以下の炭素繊維からなる。負極には、直径10mm、厚さ0.5mmの金属リチウム(田中貴金属製)を用いた。これらを用いて図1に示したリチウム空気電池を作製した。まず、SUS製のケーシング28に負極21を設置し、正極22との間にはリチウム伝導性の固体電解質25(OHARA製)を設置した。負極21と固体電解質25との間には、イオン伝導媒体24として非水電解液(電解液A)5mLを注入した。電解液Aには、1Mのリチウムテトラフルオロスルフォニルイミド(以下LiTFSI)を支持塩として含む、エチレンカーボネート30質量部とジエチルカーボネート70質量部からなる溶液(関東化学製)を用いた。次に、アセトニトリル(以下AN)に0.5MのLiTFSIを含む非水電解液を調製した(電解液B)。この非水電解液200μLを固体電解質25と正極22の間に注入した。正極22上から空気が流通可能な押さえ部材31で押し付けることにより、セルを固定した。このようにして実施例1のリチウム空気電池を得た。なお、図示しないが、ケーシング28は正極22と接触する上部と負極21と接触する下部とに分離可能であり、絶縁樹脂の介在により、正極22と負極21とは電気的に絶縁されている。
このようにして得られたリチウム空気電池を、アスカ電子製の充放電装置(型名5V/100MA)にセットし、正極22と負極21との間で0.63mA(200μA/cm2)の電流を流して放電電位が2.0V以下となるまで放電した。この放電試験は、25℃で行った。
電解液Bの電解液溶媒を、50体積%のイオン液体(N,N−ジエチル−N−メチル−N−(2−メトキシエチル)アンモニウムビス(トリフルオロメチルスルホニル)イミド,以下、DEME−TFSI)を含む混合溶媒とした以外は実施例1と同様に作製したリチウム空気電池を実施例2とした。実施例1と同様の条件で放電を行った。
電流密度を10μA/cm2として放電試験を実施したものを実施例3とした。
電解液Bの電解液溶媒をDEME−TFSIのみとした以外は実施例1と同様に作製したリチウム空気電池を比較例1とした。また、電解液Bの電解液溶媒をジメチルスルホキシド(以下、DMSO)のみとした以外は実施例1と同様に作製したリチウム空気電池を比較例2とした。比較例1、2についても、放電時の電流密度を10μA/cm2として放電試験を実施した。
図2は、実施例1、2の放電試験における電圧と電池容量の変化を表すグラフである。図3は、実施例3及び比較例1、2の放電試験における電圧と電池容量の変化を表すグラフである。図2に示すように、実施例1、2では、200μA/cm2の電流密度において2.4mAh/cm2を超える高容量の放電が可能であることがわかった。これは、正極に結着材の不要な炭素繊維からなるカーボンペーパを用い、リチウムイオン伝導性と酸素溶解性が高いアセトニトリルを電解液溶媒に全量あるいは一部含むためであると考えられた。また、図3に示すように。比較例1では、電解液溶媒にDEME−TFSIのみを用いているため放電容量は0.002mAh/cm2とほとんど得られなかった。また、比較例2では、電子供与性の高いDMSOを使用しているため、非特許文献1に記載のとおり、比較例1と比べて高い放電容量が得られたが、実施例3と比較すると低い放電容量であった。このように、正極にカーボンペーパーを用い、正極側の非水電解液にアセトニトリルを含む実施例1〜3では、放電容量を高めることができることがわかった。特に、非特許文献1において放電容量が大きいDMSOでは本実施例では小さく、非特許文献1において放電容量が小さいアセトニトリルで本実施例は大きい結果となり、正極部材と電解液との特異な組み合わせがあることがわかった。
Claims (6)
- リチウムを吸蔵放出する負極活物質を有する負極と、
結着材を含まない炭素材料からなり、酸素を正極活物質とする正極と、
前記正極に接触しアセトニトリルを含む非水電解液と、
を備えたリチウム空気電池。 - 前記正極は、前記結着材を含まない炭素材料として直径5μm以上20μm以下の炭素繊維を含む、請求項1に記載のリチウム空気電池。
- 前記正極は、前記結着材を含まない炭素材料としてカーボンペーパーからなる、請求項1又は2に記載のリチウム空気電池。
- 前記非水電解液は、60体積%以下のイオン液体を含む、請求項1〜3のいずれか1項に記載のリチウム空気電池。
- 前記負極は、前記負極活物質としてリチウム金属を有し、
前記正極と前記負極との間にリチウムイオンを伝導する固体電解質を備える、請求項1〜4のいずれか1項に記載のリチウム空気電池。 - 前記負極と前記固体電解質との間には、前記正極側の非水電解液とは異なるイオン伝導媒体を含む、請求項5に記載のリチウム空気電池。
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