JP2006286414A - 非水電解質空気電池 - Google Patents
非水電解質空気電池 Download PDFInfo
- Publication number
- JP2006286414A JP2006286414A JP2005105172A JP2005105172A JP2006286414A JP 2006286414 A JP2006286414 A JP 2006286414A JP 2005105172 A JP2005105172 A JP 2005105172A JP 2005105172 A JP2005105172 A JP 2005105172A JP 2006286414 A JP2006286414 A JP 2006286414A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- nonaqueous electrolyte
- positive electrode
- ability
- air battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims description 16
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910010586 LiFeO 2 Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910016583 MnAl Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000010485 coping Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 44
- -1 polytetrafluoroethylene Polymers 0.000 description 41
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 8
- 239000003115 supporting electrolyte Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000005001 laminate film 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
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002129 La0.6Ca0.4CoO3 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 description 1
- ROYOLNQPXVHWNE-UHFFFAOYSA-N [Co].[Ca].[La] Chemical compound [Co].[Ca].[La] ROYOLNQPXVHWNE-UHFFFAOYSA-N 0.000 description 1
- GGGMJWBVJUTTLO-UHFFFAOYSA-N [Co]=O.[Sr].[La] Chemical compound [Co]=O.[Sr].[La] GGGMJWBVJUTTLO-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- GPCXOTFNQZKHSR-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[La+3].[K+].[Mn](=O)(=O)([O-])[O-] Chemical compound [Mn](=O)(=O)([O-])[O-].[La+3].[K+].[Mn](=O)(=O)([O-])[O-] GPCXOTFNQZKHSR-UHFFFAOYSA-N 0.000 description 1
- JOCCKLUWAJCUFY-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[La+3].[Na+].[Mn](=O)(=O)([O-])[O-] Chemical compound [Mn](=O)(=O)([O-])[O-].[La+3].[Na+].[Mn](=O)(=O)([O-])[O-] JOCCKLUWAJCUFY-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
- ZPIRDTOMKBAWBG-UHFFFAOYSA-N [Rb+].[Mn](=O)(=O)([O-])[O-].[La+3].[Mn](=O)(=O)([O-])[O-] Chemical compound [Rb+].[Mn](=O)(=O)([O-])[O-].[La+3].[Mn](=O)(=O)([O-])[O-] ZPIRDTOMKBAWBG-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910021320 cobalt-lanthanum-strontium oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 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
- 239000006232 furnace black Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 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
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 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
- 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
- 239000004745 nonwoven fabric Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 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
- 229920001187 thermosetting polymer Polymers 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Inert Electrodes (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
【解決手段】 正極と、負極と、非水電解質と、前記正極に酸素を供給するための空気孔を備えるケースとを具備した非水電解質空気電池において、前記正極が組成の異なる2つの層からなり、空気穴側に少なくとも酸素還元能を有する層、負極側に少なくともリチウムイオン吸蔵能を有する層が、それぞれ配置されることを特徴とする非水電解質空気電池。
【選択図】 図1
Description
正極は、正極集電体と、この正極集電体に担持された正極層とを含む。正極層は、各々組成の異なる2つの層からなり、空気穴側に少なくとも酸素還元能を有する層、負極側に少なくともリチウムイオン吸蔵能を有する層が、それぞれ配置されている。
非水電解質液としては、従来よりリチウムイオン二次電池の電解液として用いられる各種非水電解液を用いることができる。例えば、有機溶媒に支持電解質を溶解した有機溶媒系非水電解液や、常温溶融塩に支持電解質を溶解した常温溶融塩系非水電解液や、あるいは高分子材料と有機溶媒系/常温溶融塩系非水電解液からなるゲル状電解液などを使用することができる。
前記負極は、負極集電体と、前記負極集電体に担持される負極層とを含む。前記負極層は、負極活物質と結着剤からなるものを用いることができる。負極活物質は、少なくともリチウムイオン放出能を備えていれば良く、前記負極活物質としては、従来よりリチウム一次電池およびリチウムイオン二次電池の負極材料として用いられる各種負極活物質を用いることができる。
この容器は、例えば、金属板、樹脂層を有するシート等から形成することができる。
以下の実施例の電池は、当然ながら上述した図1の電池を実現しているのであって、ここでは、図1の説明で紹介できなかった詳細な説明を中心に説明している。
酸素還元能を有する層の原料としてケッチェンブラック80重量%、La0.6Ca0.4CoO310重量%およびPTFE10重量%を用い、リチウムイオン吸蔵能を有する層の原料として五酸化バナジウム80重量%、アセチレンブラック10重量%およびPTFE10重量%を用い、さらに非水電解質としてEMITFSIに1M/Lの割合でLiTFSIを溶解した常温溶融塩系非水電解質を用いたこと以外は、実施例1と同様の手法により非水電解質空気電池を作製した。得られた電池を実施例1と同じ条件で放電試験を実施したところ、放電時間は120時間であった。
酸素還元能を有する層の原料としてアセチレンブラック(比表面積650m2/g)80重量%、Rb0.2La0.8MnO310重量%およびPTFE10重量%を用い、リチウムイオン吸蔵能を有する層の原料としてLiFeO280重量%、アセチレンブラック10重量%およびPTFE10重量%を用い、さらに非水電解質としてEMIBF4に1M/Lの割合でLiBOBを溶解した常温溶融塩系非水電解質を用いたこと以外は、実施例1と同様の手法により非水電解質空気電池を作製した。得られた電池を実施例1と同じ条件で放電試験を実施したところ、放電時間は110時間であった。
正極として、ケッチェンブラック80重量%、コバルトフタロシアニン10重量%、PTFE10重量%を混合し、厚さ200μmのシート状に形成した。前記シートを用いて正極を作成したこと以外は、実施例1と同様の手法により非水電解質空気電池を作製した。得られた電池を実施例1と同じ条件で放電試験を実施したところ、放電時間は1分であった。パルス放電時に電圧が2Vを下回ったのが原因と考えられる。
正極として、二酸化マンガン80重量%、アセチレンブラック10重量%、PTFE10%を混合し、厚さ200μmのシート状に形成した。前記シートを用いて正極を作成したこと以外は、実施例1と同様の手法により非水電解質空気電池を作製した。得られた電池を実施例1と同じ条件で放電試験を実施したところ、放電時間は40時間であった。空気電池としての容量が少ないことが原因と考えられる。
2…電極群、
3…正極端子、
4…負極端子
Claims (5)
- 正極と、負極と、この正極及び負極の間に形成された非水電解質と、前記正極に酸素を供給するための空気孔を備えるケースとを具備した非水電解質空気電池において、前記正極が組成の異なる2つの層からなり、空気穴側に少なくとも酸素還元能を有する層、負極側に少なくともリチウムイオン吸蔵能を有する層がそれぞれ配置され、前記リチウムイオン吸蔵能を有する層は、リチウムイオンを2.0V以上2.9V以下(vs.Li)で吸蔵する能力を有する活物質と、導電剤と、結着剤からなることを特徴とする非水電解質空気電池。
- 前記リチウムイオンを吸蔵する能力を有する活物質がリチウムイオンの可逆な吸蔵・放出能を有することを特徴とする、請求項1記載の非水電解質空気電池。
- 前記リチウムイオンを吸蔵放出する活物質が、マンガン酸化物(MnO2)、五酸化バナジウム(V2O5)、酸化銅(CuO)、V2O5/TeO2、V2O5/P2O5、V2O5/B2O3、CuV2O6、Cu2V2O7、Cr2O5、Cr3O8、TiS2、LiFeO2、クロム酸化物(Cr3O8,CrO2)、三酸化モリブデン(MoO3)、二酸化チタン(TiO2)、マンガン複合酸化物(MnTixOy、MnAlxOy、MnCaxOy、MnZnxOy)より選ばれる遷移金属酸化物であることを特徴とする請求項2記載の非水電解質空気電池。
- 前記リチウムイオンの吸蔵能を有する活物質が前記リチウムイオン吸蔵能を有する層中に70重量%以上含有されることを特徴とする請求項1に記載の非水電解質空気電池。
- 前記酸素還元能を有する層は、少なくとも比表面積が600m2/g以上の炭素質物と、結着剤からなることを特徴とする請求項1に記載の非水電解質空気電池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005105172A JP4575212B2 (ja) | 2005-03-31 | 2005-03-31 | 非水電解質空気電池 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005105172A JP4575212B2 (ja) | 2005-03-31 | 2005-03-31 | 非水電解質空気電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2006286414A true JP2006286414A (ja) | 2006-10-19 |
JP4575212B2 JP4575212B2 (ja) | 2010-11-04 |
Family
ID=37408102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005105172A Expired - Fee Related JP4575212B2 (ja) | 2005-03-31 | 2005-03-31 | 非水電解質空気電池 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4575212B2 (ja) |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007072713A1 (ja) * | 2005-12-22 | 2007-06-28 | Fuji Jukogyo Kabushiki Kaisha | 電池又はキャパシタ用金属リチウム箔 |
JP2008112724A (ja) * | 2006-10-06 | 2008-05-15 | Toyota Central R&D Labs Inc | 正極用触媒及びリチウム空気二次電池 |
JP2008270166A (ja) * | 2007-03-29 | 2008-11-06 | Toyota Central R&D Labs Inc | 空気電池 |
JP2009283411A (ja) * | 2008-05-26 | 2009-12-03 | Toyota Motor Corp | 空気電池 |
JP2010003694A (ja) * | 2008-06-20 | 2010-01-07 | Univ Dayton | 高いイオン輸送能力と触媒活性を有する固体電解質を組み込んだリチウム−空気電池 |
JP2010056026A (ja) * | 2008-08-29 | 2010-03-11 | Ohara Inc | リチウム電池用セパレーターおよびリチウム電池。 |
WO2010061451A1 (ja) * | 2008-11-27 | 2010-06-03 | トヨタ自動車株式会社 | 空気二次電池 |
CN101960664A (zh) * | 2008-12-25 | 2011-01-26 | 丰田自动车株式会社 | 锂空气电池 |
US7887957B2 (en) | 2007-06-01 | 2011-02-15 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Non-aqueous air battery and catalyst therefor |
WO2011086701A1 (ja) * | 2010-01-18 | 2011-07-21 | トヨタ自動車株式会社 | リチウム空気電池 |
CN102637863A (zh) * | 2012-04-16 | 2012-08-15 | 佛山市邦普循环科技有限公司 | 一种锂空气电池的正极材料及其制备方法 |
US8252451B2 (en) | 2008-10-08 | 2012-08-28 | Toyota Jidosha Kabushiki Kaisha | Battery electrode and battery electrode manufacturing method |
WO2012114453A1 (ja) * | 2011-02-22 | 2012-08-30 | トヨタ自動車株式会社 | 非水電解質空気電池 |
WO2012114175A1 (en) | 2011-02-24 | 2012-08-30 | Toyota Jidosha Kabushiki Kaisha | Air electrode for air battery, method of producing same, and air battery |
JP2012238591A (ja) * | 2011-04-27 | 2012-12-06 | Sumitomo Chemical Co Ltd | 空気二次電池用正極触媒及び空気二次電池 |
US8415074B2 (en) | 2007-09-04 | 2013-04-09 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Nonaqueous electrolyte battery |
JP2013084430A (ja) * | 2011-10-07 | 2013-05-09 | Toyota Motor Corp | 空気電池用電解液 |
US8465877B2 (en) | 2008-03-24 | 2013-06-18 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Alkali metal air battery |
WO2013174770A1 (fr) * | 2012-05-25 | 2013-11-28 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Cathode pour batterie lithium-air, comportant une structure bi-couches de catalyseurs differents et batterie lithium-air comprenant cette cathode |
JPWO2013054418A1 (ja) * | 2011-10-13 | 2015-03-30 | トヨタ自動車株式会社 | 空気電池、当該空気電池を備える移動体、及び空気電池の使用方法 |
JPWO2013051309A1 (ja) * | 2011-10-07 | 2015-03-30 | トヨタ自動車株式会社 | リチウム空気電池用の電解液 |
US9099758B2 (en) | 2008-06-20 | 2015-08-04 | University Of Dayton | Lithium-air cell incorporating lithium aluminum germanium phosphate cathode |
US9236640B2 (en) | 2009-09-24 | 2016-01-12 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Gas battery comprising carbon dioxide gas as a positive electrode active material and method of use of gas battery |
CN111244413A (zh) * | 2020-01-16 | 2020-06-05 | 河南工业大学 | 一种lto/cvo复合材料及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04192270A (ja) * | 1990-11-26 | 1992-07-10 | Seiko Epson Corp | 空気電池用空気電極の作製方法 |
JP2005019145A (ja) * | 2003-06-25 | 2005-01-20 | Toshiba Battery Co Ltd | 空気電池 |
-
2005
- 2005-03-31 JP JP2005105172A patent/JP4575212B2/ja not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04192270A (ja) * | 1990-11-26 | 1992-07-10 | Seiko Epson Corp | 空気電池用空気電極の作製方法 |
JP2005019145A (ja) * | 2003-06-25 | 2005-01-20 | Toshiba Battery Co Ltd | 空気電池 |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007072713A1 (ja) * | 2005-12-22 | 2007-06-28 | Fuji Jukogyo Kabushiki Kaisha | 電池又はキャパシタ用金属リチウム箔 |
US8685117B2 (en) | 2005-12-22 | 2014-04-01 | Fuji Jukogyo Kabushiki Kaisha | Lithium metal foil for battery or capacitor |
JP2008112724A (ja) * | 2006-10-06 | 2008-05-15 | Toyota Central R&D Labs Inc | 正極用触媒及びリチウム空気二次電池 |
JP2008270166A (ja) * | 2007-03-29 | 2008-11-06 | Toyota Central R&D Labs Inc | 空気電池 |
US7887957B2 (en) | 2007-06-01 | 2011-02-15 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Non-aqueous air battery and catalyst therefor |
US8415074B2 (en) | 2007-09-04 | 2013-04-09 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Nonaqueous electrolyte battery |
US8465877B2 (en) | 2008-03-24 | 2013-06-18 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Alkali metal air battery |
JP2009283411A (ja) * | 2008-05-26 | 2009-12-03 | Toyota Motor Corp | 空気電池 |
JP2010003694A (ja) * | 2008-06-20 | 2010-01-07 | Univ Dayton | 高いイオン輸送能力と触媒活性を有する固体電解質を組み込んだリチウム−空気電池 |
US9099758B2 (en) | 2008-06-20 | 2015-08-04 | University Of Dayton | Lithium-air cell incorporating lithium aluminum germanium phosphate cathode |
US9178255B2 (en) | 2008-06-20 | 2015-11-03 | University Of Dayton | Lithium-air cells incorporating solid electrolytes having enhanced ionic transport and catalytic activity |
JP2010056026A (ja) * | 2008-08-29 | 2010-03-11 | Ohara Inc | リチウム電池用セパレーターおよびリチウム電池。 |
US8252451B2 (en) | 2008-10-08 | 2012-08-28 | Toyota Jidosha Kabushiki Kaisha | Battery electrode and battery electrode manufacturing method |
WO2010061451A1 (ja) * | 2008-11-27 | 2010-06-03 | トヨタ自動車株式会社 | 空気二次電池 |
JP5104942B2 (ja) * | 2008-11-27 | 2012-12-19 | トヨタ自動車株式会社 | 空気二次電池 |
CN101821897A (zh) * | 2008-11-27 | 2010-09-01 | 丰田自动车株式会社 | 空气二次电池 |
CN101960664A (zh) * | 2008-12-25 | 2011-01-26 | 丰田自动车株式会社 | 锂空气电池 |
US8741492B2 (en) | 2008-12-25 | 2014-06-03 | Toyota Jidosha Kabushiki Kaisha | Lithium air battery |
US9236640B2 (en) | 2009-09-24 | 2016-01-12 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Gas battery comprising carbon dioxide gas as a positive electrode active material and method of use of gas battery |
CN102714339A (zh) * | 2010-01-18 | 2012-10-03 | 丰田自动车株式会社 | 锂空气电池 |
WO2011086701A1 (ja) * | 2010-01-18 | 2011-07-21 | トヨタ自動車株式会社 | リチウム空気電池 |
JP5299523B2 (ja) * | 2010-01-18 | 2013-09-25 | トヨタ自動車株式会社 | カチオン判定方法 |
US9231269B2 (en) | 2011-02-22 | 2016-01-05 | Toyota Jidosha Kabushiki Kaisha | Non-aqueous electrolyte air battery |
CN103370830A (zh) * | 2011-02-22 | 2013-10-23 | 丰田自动车株式会社 | 非水电解质空气电池 |
WO2012114453A1 (ja) * | 2011-02-22 | 2012-08-30 | トヨタ自動車株式会社 | 非水電解質空気電池 |
WO2012114175A1 (en) | 2011-02-24 | 2012-08-30 | Toyota Jidosha Kabushiki Kaisha | Air electrode for air battery, method of producing same, and air battery |
JP2012238591A (ja) * | 2011-04-27 | 2012-12-06 | Sumitomo Chemical Co Ltd | 空気二次電池用正極触媒及び空気二次電池 |
JPWO2013051309A1 (ja) * | 2011-10-07 | 2015-03-30 | トヨタ自動車株式会社 | リチウム空気電池用の電解液 |
JP2013084430A (ja) * | 2011-10-07 | 2013-05-09 | Toyota Motor Corp | 空気電池用電解液 |
JPWO2013054418A1 (ja) * | 2011-10-13 | 2015-03-30 | トヨタ自動車株式会社 | 空気電池、当該空気電池を備える移動体、及び空気電池の使用方法 |
CN102637863A (zh) * | 2012-04-16 | 2012-08-15 | 佛山市邦普循环科技有限公司 | 一种锂空气电池的正极材料及其制备方法 |
FR2991103A1 (fr) * | 2012-05-25 | 2013-11-29 | Commissariat Energie Atomique | Cathode pour batterie lithium-air, comportant une structure bi-couches de catalyseurs differents et batterie lithium-air comprenant cette cathode |
WO2013174770A1 (fr) * | 2012-05-25 | 2013-11-28 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Cathode pour batterie lithium-air, comportant une structure bi-couches de catalyseurs differents et batterie lithium-air comprenant cette cathode |
CN111244413A (zh) * | 2020-01-16 | 2020-06-05 | 河南工业大学 | 一种lto/cvo复合材料及其制备方法 |
CN111244413B (zh) * | 2020-01-16 | 2021-06-29 | 河南工业大学 | 一种lto/cvo复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4575212B2 (ja) | 2010-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4575212B2 (ja) | 非水電解質空気電池 | |
JP3797197B2 (ja) | 非水電解質二次電池 | |
JP5253905B2 (ja) | 非水電解液および非水電解液二次電池 | |
JP4042034B2 (ja) | 非水電解質電池 | |
US8741492B2 (en) | Lithium air battery | |
JP6156939B2 (ja) | リチウムイオン二次電池 | |
US20090053594A1 (en) | Rechargeable air battery and manufacturing method | |
KR101735857B1 (ko) | 고전압 리튬 이차전지 | |
JP2010123287A (ja) | 非水電解液および非水電解液二次電池 | |
JP2009152188A (ja) | 正極活物質、正極および非水電解質二次電池 | |
CN102376946A (zh) | 正极活性物质和包括所述正极活性物质的锂电池 | |
JP2007207675A (ja) | イオン性液体を用いたリチウム二次電池 | |
JP6746506B2 (ja) | 非水電解液二次電池 | |
JP2005267940A (ja) | 非水電解質電池 | |
KR20010007465A (ko) | 비수성 전해액 2차 전지 | |
JP4223705B2 (ja) | 非水電解質電池およびその製造方法 | |
JP2004119278A (ja) | 非水電解質空気電池 | |
JP2010092673A (ja) | 非水電解質二次電池 | |
JP2008305688A (ja) | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 | |
JP2010199083A (ja) | リチウム二次電池 | |
JP2017076612A (ja) | リチウム空気二次電池 | |
JP2005293960A (ja) | リチウムイオン二次電池用負極およびリチウムイオン二次電池 | |
JP2011071017A (ja) | リチウム二次電池 | |
JP2002175836A (ja) | 非水電解質電池 | |
JP2002015720A (ja) | 非水電解質二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061109 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100402 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100528 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100723 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100819 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 4575212 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130827 Year of fee payment: 3 |
|
LAPS | Cancellation because of no payment of annual fees |