WO2022091407A1 - リチウム2次電池 - Google Patents
リチウム2次電池 Download PDFInfo
- Publication number
- WO2022091407A1 WO2022091407A1 PCT/JP2020/041040 JP2020041040W WO2022091407A1 WO 2022091407 A1 WO2022091407 A1 WO 2022091407A1 JP 2020041040 W JP2020041040 W JP 2020041040W WO 2022091407 A1 WO2022091407 A1 WO 2022091407A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- secondary battery
- lithium
- lithium secondary
- positive electrode
- Prior art date
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 146
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 112
- 239000007773 negative electrode material Substances 0.000 claims abstract description 23
- 230000003746 surface roughness Effects 0.000 claims abstract description 15
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 description 31
- 239000010949 copper Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 24
- 229910003002 lithium salt Inorganic materials 0.000 description 18
- 159000000002 lithium salts Chemical class 0.000 description 18
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000008151 electrolyte solution Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 150000003839 salts Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- UGKREBHYJCJQTQ-UHFFFAOYSA-N 4-methyl-5-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C(F)(F)F UGKREBHYJCJQTQ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005275 alloying Methods 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
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GIPIUENNGCQCIT-UHFFFAOYSA-K cobalt(3+) phosphate Chemical class [Co+3].[O-]P([O-])([O-])=O GIPIUENNGCQCIT-UHFFFAOYSA-K 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004381 surface treatment Methods 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Definitions
- the present invention relates to a lithium secondary battery.
- a secondary battery that charges and discharges by moving metal ions between a positive electrode and a negative electrode is known to exhibit high voltage and high energy density, and is typically a lithium ion secondary battery. It has been known.
- an active material capable of holding lithium is introduced into the positive electrode and the negative electrode, and charging / discharging is performed by exchanging lithium ions between the positive electrode active material and the negative electrode active material.
- a lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode has been developed.
- Patent Document 1 describes a high energy density, high power lithium metal anode having a volumetric energy density of greater than 1000 Wh / L and / or a mass energy density of greater than 350 Wh / kg when discharged at room temperature at a rate of at least 1 C. Secondary batteries are disclosed. Patent Document 1 discloses the use of an ultrathin lithium metal anode in order to realize such a lithium metal anode secondary battery.
- Patent Document 2 in a lithium secondary battery including a positive electrode, a negative electrode, a separation film interposed between them, and an electrolyte, in the negative electrode, metal particles are formed on a negative electrode current collector, and the negative electrode is charged.
- a lithium secondary battery that is moved from the positive electrode and forms a lithium metal on the negative electrode current collector in the negative electrode is disclosed.
- Patent Document 2 provides a lithium secondary battery in which such a lithium secondary battery solves a problem caused by the reactivity of a lithium metal and a problem generated in the assembly process, and has improved performance and life. Discloses what can be done.
- a typical secondary battery that charges and discharges by exchanging metal ions between a positive electrode active material and a negative electrode active material does not have sufficient energy density.
- a conventional lithium metal secondary battery that holds lithium by precipitating lithium metal on the surface of the negative electrode as described in the above patent document has a dendrite shape on the surface of the negative electrode by repeating charging and discharging. Lithium metal is likely to be formed, and short circuit and capacity reduction are likely to occur. As a result, the cycle characteristics are not sufficient.
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a lithium secondary battery having a high energy density and excellent cycle characteristics.
- the lithium secondary battery according to the embodiment of the present invention includes a positive electrode and a negative electrode having no negative electrode active material.
- the negative electrode is Cu having a maximum surface roughness Rz of 1.0 ⁇ m or less and an orientation plane of (200) plane or (220) plane.
- the negative electrode thereof has a surface roughness maximum height Rz of 1.0 ⁇ m or less and an orientation plane of (200) plane or (220) plane. It is called Cu. This makes it possible to improve the cycle characteristics of the secondary battery.
- Cu as a negative electrode is formed by rolling. This makes it possible to use Cu having a (200) plane or a (220) plane as an orientation plane, which is suitable for a negative electrode.
- the lithium secondary battery is a lithium secondary battery in which lithium metal is deposited on the surface of a negative electrode and charged / discharged is performed by dissolving the deposited lithium. According to such an embodiment, the energy density is further increased.
- the lithium secondary battery preferably has no lithium foil formed on the surface of the negative electrode before the initial charge. According to such an aspect, since it is not necessary to use a highly flammable lithium metal in the production, the safety and productivity are further improved.
- the lithium secondary battery preferably has an energy density of 350 Wh / kg or more.
- the present embodiments will be described in detail with reference to the drawings as necessary.
- the same elements are designated by the same reference numerals, and duplicate description will be omitted.
- the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified.
- the dimensional ratios in the drawings are not limited to the ratios shown.
- FIG. 1 is a schematic cross-sectional view of a lithium secondary battery according to the first embodiment.
- the lithium secondary battery 100 of the first embodiment has a positive electrode 120, a negative electrode 130 having no negative electrode active material, and a separator 140 arranged between the positive electrode 120 and the negative electrode 130.
- the positive electrode 120 has a positive electrode current collector 110 on a surface opposite to the surface facing the separator 140.
- the negative electrode 130 does not have a negative electrode active material. It is difficult to increase the energy density of a lithium secondary battery including a negative electrode having a negative electrode active material due to the presence of the negative electrode active material. On the other hand, since the lithium secondary battery 100 of the present embodiment includes the negative electrode 130 having no negative electrode active material, such a problem does not occur. That is, the lithium secondary battery 100 of the present embodiment has a high energy density because lithium metal is deposited on the surface of the negative electrode 130 and the deposited lithium metal is electrolytically eluted to charge and discharge.
- lithium metal precipitates on the surface of the negative electrode means that the lithium metal is formed on the surface of the negative electrode and at least one surface of the solid electrolyte interface (SEI) layer described later formed on the surface of the negative electrode.
- SEI solid electrolyte interface
- the lithium metal may be deposited on the surface of the negative electrode 130 (the interface between the negative electrode 130 and the separator 140), for example.
- negative electrode active material means a material for holding lithium ions or lithium metal (hereinafter, also referred to as “carrier metal”), which are charge carriers in a battery, in the negative electrode 130, and is a carrier metal. It may be paraphrased as the host substance of.
- carrier metal lithium metal
- the mechanism of such holding is not particularly limited, and examples thereof include intercalation, alloying, and occlusion of metal clusters.
- the negative electrode active material is not particularly limited, and examples thereof include carbon-based substances, metal oxides, metals, alloys, and the like.
- the carbon-based substance is not particularly limited, and examples thereof include graphene, graphite, hard carbon, mesoporous carbon, carbon nanotubes, and carbon nanohorns.
- the metal oxide is not particularly limited, and examples thereof include titanium oxide-based compounds, tin oxide-based compounds, lithium oxide-based compounds, and cobalt oxide-based compounds.
- the metal or alloy is not particularly limited as long as it can be alloyed with the carrier metal, and examples thereof include silicon, germanium, tin, lead, aluminum, gallium, lithium, and alloys containing these.
- Cu copper having no negative electrode active material
- the Cu of the negative electrode 130 of the present embodiment is obtained by subjecting a known surface treatment to Cu whose orientation plane is (200) plane or (220) plane by rolling a copper plate into a foil shape. Use. Further, as this Cu, one having a maximum surface roughness Rz of 1.0 ⁇ m or less is used. The maximum height Rz of the surface roughness indicates the difference in height between the position where the height is the highest and the position where the height is the lowest on the Cu surface. Although the detailed mechanism of action is unknown, by adopting a specific orientation plane (200) plane or (220) plane of Cu and controlling the surface roughness Rz, as shown in Examples described later, it is secondary. It has been confirmed that the cycle characteristics of the battery can be improved.
- the Cu orientation plane corresponds to the location where the highest peak intensity was obtained when the rolled Cu crystal structure was evaluated by X-ray diffraction measurement (XRD) with a characteristic X-ray wavelength of 1.5406 ⁇ . Defined as a face. That is, the orientation plane of Cu is determined based on whether the obtained peak intensity is obtained at a position corresponding to the (111) plane, the (200) plane, or the (220) plane. For example, when the measurement result as shown in FIG. 4 is obtained, the peaks P1, P2, and P3 correspond to the orientation planes of the (111) plane, the (200) plane, and the (220) plane, respectively, and are the highest. It is the peak P2 corresponding to the (200) plane that the peak intensity is obtained. Therefore, it can be said that the orientation plane of Cu from which such a measurement result can be obtained is the (200) plane.
- XRD X-ray diffraction measurement
- the negative electrode does not have a negative electrode active material
- the content of the negative electrode active material in the negative electrode is 10% by mass or less with respect to the entire negative electrode.
- the content of the negative electrode active material in the negative electrode is preferably 5.0% by mass or less, 1.0% by mass or less, or 0.1% by mass or less with respect to the entire negative electrode. , 0.0% by mass or less.
- the fact that the lithium secondary battery 100 includes a negative electrode having no negative electrode active material means that the lithium secondary battery 100 is an anode-free secondary battery, a zero anode secondary battery, or an anode in the sense that it is generally used. It means that it is a less secondary battery.
- An anode-free secondary battery is a battery system that does not contain any lithium metal or negative electrode active material and is composed only of a current collector on the negative electrode side.
- the capacity of the negative electrode active material possessed by the negative electrode is set to be the same as the capacity of the positive electrode. Therefore, even when the capacity of the negative electrode active material in the negative electrode 130 is smaller than the capacity of the positive electrode 120, for example, 20% or less, 15% or less, 10% or less, or 5% or less, "the negative electrode is the negative electrode active". It means "has no substance”.
- the average thickness of the negative electrode 130 is preferably 4 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 18 ⁇ m or less, and further preferably 6 ⁇ m or more and 15 ⁇ m or less. According to such an embodiment, the volume occupied by the negative electrode 130 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
- the lithium secondary battery 100 Since the positive electrode 120 contains a positive electrode active material, the lithium secondary battery 100 has excellent stability and a high output voltage.
- the “positive electrode active material” means a substance for retaining lithium ions in the positive electrode 120, and may be paraphrased as a host material for lithium ions.
- Such positive electrode active material is not particularly limited, and examples thereof include metal oxides and metal phosphates.
- the metal oxide is not particularly limited, and examples thereof include a cobalt oxide-based compound, a manganese oxide-based compound, and a nickel oxide-based compound.
- the metal phosphate is not particularly limited, and examples thereof include iron phosphate compounds and cobalt phosphate compounds.
- the positive electrode active material as described above one type may be used alone or two or more types may be used in combination.
- the positive electrode 120 may contain components other than the above-mentioned positive electrode active material. Such components include, but are not limited to, known conductive aids, binders, solid polymer electrolytes, and inorganic solid electrolytes.
- the conductive auxiliary agent in the positive electrode 120 is not particularly limited, and examples thereof include carbon black, single-wall carbon nanotubes (SWCNT), multi-wall carbon nanotubes (MWCNT), carbon nanofibers (CF), and acetylene black.
- the binder is not particularly limited, and examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, acrylic resin, and polyimide resin.
- the content of the positive electrode active material in the positive electrode 120 may be, for example, 50% by mass or more and 100% by mass or less with respect to the entire positive electrode 120.
- the content of the conductive auxiliary agent may be, for example, 0.5% by mass or more and 30% by mass or less with respect to the entire positive electrode 120.
- the content of the binder may be, for example, 0.5% by mass or more and 30% by mass or less with respect to the entire positive electrode 120.
- the total content of the solid polymer electrolyte and the inorganic solid electrolyte may be, for example, 0.5% by mass or more and 30% by mass or less with respect to the entire positive electrode 120.
- a positive electrode current collector 110 is formed on one side of the positive electrode 120.
- the positive electrode current collector 110 is not particularly limited as long as it is a conductor that does not react with lithium ions in the battery. Examples of such a positive electrode current collector include aluminum.
- the average thickness of the positive electrode current collector 110 is preferably 4 ⁇ m or more and 20 ⁇ m or less, more preferably 5 ⁇ m or more and 18 ⁇ m or less, and further preferably 6 ⁇ m or more and 15 ⁇ m or less. According to such an embodiment, the volume occupied by the positive electrode current collector 110 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
- the separator 140 is a member for ensuring the ionic conductivity of lithium ions, which are charge carriers between the positive electrode 120 and the negative electrode 130, while preventing the battery from short-circuiting by separating the positive electrode 120 and the negative electrode 130. It is made of a material that does not have electron conductivity and does not react with lithium ions.
- the separator 140 also plays a role of holding the electrolytic solution.
- the separator 140 is not limited as long as it plays the above role, but is composed of, for example, porous polyethylene (PE), polypropylene (PP), or a laminated structure thereof.
- the separator 140 may be covered with a separator coating layer.
- the separator coating layer may cover both sides of the separator 140, or may cover only one side.
- the separator coating layer is not particularly limited as long as it is a member having ionic conductivity and does not react with lithium ions, but it is preferable that the separator 140 and the layer adjacent to the separator 140 can be firmly adhered to each other. ..
- the separator coating layer is not particularly limited, and is, for example, polyvinylidene fluoride (PVDF), a mixture of styrene-butadiene rubber and carboxymethyl cellulose (SBR-CMC), polyacrylic acid (PAA), and lithium polyacrylic acid.
- binders such as (Li-PAA), polyimide (PI), polyamideimide (PAI), and aramid.
- binders such as (Li-PAA), polyimide (PI), polyamideimide (PAI), and aramid.
- inorganic particles such as silica, alumina, titania, zirconia, magnesium oxide, magnesium hydroxide, and lithium nitrate may be added to the binder.
- the average thickness of the separator 140 is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, and further preferably 15 ⁇ m or less. According to such an embodiment, the volume occupied by the separator 140 in the lithium secondary battery 100 is reduced, so that the energy density of the lithium secondary battery 100 is further improved.
- the average thickness of the separator 140 is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more. According to such an aspect, the positive electrode 120 and the negative electrode 130 can be more reliably isolated, and the short circuit of the battery can be further suppressed.
- the lithium secondary battery 100 may have an electrolytic solution.
- the electrolytic solution may be infiltrated into the separator 140, or the electrolytic solution may be sealed together with the lithium secondary battery 100 as a finished product.
- the electrolytic solution is a solution containing an electrolyte and a solvent and having ionic conductivity, and acts as a conductive path for lithium ions. Therefore, in the lithium secondary battery 100 having an electrolytic solution, the internal resistance is further reduced, and the energy density, capacity, and cycle characteristics are further improved.
- the electrolyte is not particularly limited as long as it is a salt, and examples thereof include salts of Li, Na, K, Ca, and Mg.
- a lithium salt is preferably used as the electrolyte.
- the lithium salt is not particularly limited, but LiI, LiCl, LiBr, LiF, LiBF 4 , LiPF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN.
- LiN (SO 2 F) 2 is preferable as the lithium salt from the viewpoint of further excellent energy density, capacity, and cycle characteristics of the lithium secondary battery 100.
- the above lithium salts may be used alone or in combination of two or more.
- the solvent is not particularly limited, but is not particularly limited, for example, dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, difluoroethylene.
- the above-mentioned solvents may be used alone or in combination of two or more.
- FIG. 2 shows one usage mode of the lithium secondary battery of the present embodiment.
- a positive electrode terminal 220 and a negative electrode terminal 230 for connecting the lithium secondary battery 100 to an external circuit are bonded to the positive electrode current collector 110 and the negative electrode 130, respectively.
- the lithium secondary battery 100 is charged and discharged by connecting the negative electrode terminal 230 to one end of the external circuit and the positive electrode terminal 220 to the other end of the external circuit.
- the lithium secondary battery 100 is charged by applying a voltage between the positive electrode terminal 220 and the negative electrode terminal 230 so that a current flows from the negative electrode terminal 230 to the positive electrode terminal 220 through an external circuit. By charging the lithium secondary battery 100, precipitation of lithium metal occurs at the interface between the negative electrode 130 and the separator 140.
- a solid electrolyte interface layer (SEI layer) 210 may be formed at the interface between the negative electrode 130 and the separator 140 by initial charging.
- the SEI layer 210 to be formed is not particularly limited, and may contain, for example, an inorganic compound containing lithium, an organic compound containing lithium, and the like.
- the typical average thickness of the SEI layer is 1 nm or more and 10 ⁇ m or less.
- the lithium metal deposited during charging of the lithium secondary battery 100 may be deposited at the interface between the negative electrode 130 and the SEI layer 210, and the SEI layer 210 and the lithium metal may be deposited. It may be deposited at the interface with the separator 140.
- the lithium secondary battery 100 when the positive electrode terminal 220 and the negative electrode terminal 230 are connected, the lithium secondary battery 100 is discharged.
- the precipitation of lithium metal generated at at least one of the interface between the negative electrode 130 and the SEI layer 210 and the interface between the SEI layer 210 and the separator 140 is electrolytically eluted.
- the method for manufacturing the lithium secondary battery 100 as shown in FIG. 1 is not particularly limited as long as it can manufacture a lithium secondary battery having the above configuration, and examples thereof include the following methods. ..
- the positive electrode 120 is prepared by a known manufacturing method or by purchasing a commercially available one.
- the positive electrode 120 is manufactured, for example, as follows.
- the above-mentioned positive electrode active material, a known conductive auxiliary agent, and a known binder are mixed to obtain a positive electrode mixture.
- the compounding ratio is, for example, 50% by mass or more and 99% by mass or less of the positive electrode active material, 0.5% by mass or less of the conductive auxiliary agent, and 0.5% by mass or less of the binder with respect to the entire positive electrode mixture. It may be mass% or less.
- the obtained positive electrode mixture is applied to one side of a metal foil (for example, Al foil) as a positive electrode current collector having a predetermined thickness (for example, 5 ⁇ m or more and 1 mm or less), and press-molded.
- the obtained molded body is punched to a predetermined size by punching to obtain a positive electrode 120.
- the above-mentioned negative electrode material for example, a Cu foil of 1 ⁇ m or more and 1 mm or less, which has been subjected to rust prevention treatment, is used as the negative electrode 130.
- the separator 140 may be manufactured by a conventionally known method, or a commercially available one may be used.
- a laminated body is obtained by laminating the positive electrode 120, the separator 140, and the negative electrode 130 obtained as described above in this order.
- the lithium secondary battery 100 can be obtained by enclosing the obtained laminate together with the electrolytic solution in a closed container.
- the closed container is not particularly limited, and examples thereof include a laminated film.
- FIG. 3 is a schematic cross-sectional view of the lithium secondary battery according to the second embodiment.
- the lithium secondary battery 300 of the second embodiment has a positive electrode current collector 110, a positive electrode 120 formed on one side of the positive electrode current collector 110 and having a positive electrode active material, and a negative electrode activity.
- a negative electrode 130 having no substance and a solid electrolyte 310 arranged between the positive electrode 120 and the negative electrode 130 are provided.
- the configurations of the positive electrode current collector 110, the positive electrode 120, and the negative electrode 130 and their preferred embodiments are the same as those of the lithium secondary battery 100 of the first embodiment except for the points described later, and the lithium secondary battery 300 is the lithium 2 battery. It has the same effect as that of the next battery 100.
- Solid electrolyte In general, a battery provided with a liquid electrolyte tends to have a different physical pressure from the electrolyte to the surface of the negative electrode depending on the location due to the fluctuation of the liquid.
- the lithium secondary battery 300 since the lithium secondary battery 300 includes the solid electrolyte 310, the pressure applied from the solid electrolyte 310 to the surface of the negative electrode 130 becomes more uniform, and the shape of the carrier metal deposited on the surface of the negative electrode 130 becomes more uniform. Can be done. That is, according to such an embodiment, the carrier metal deposited on the surface of the negative electrode 130 is further suppressed from growing in a dendrite shape, so that the cycle characteristics of the lithium secondary battery 300 are further improved.
- the solid electrolyte 310 is not particularly limited as long as it is generally used for a lithium solid secondary battery, but a known material may be appropriately selected depending on the use of the lithium secondary battery 300 and the type of carrier metal. can.
- the solid electrolyte 310 preferably has ionic conductivity and no electron conductivity. Since the solid electrolyte 310 has ionic conductivity and no electron conductivity, the internal resistance of the lithium secondary battery 300 is further reduced, and short-circuiting inside the lithium secondary battery 300 is further suppressed. can do. As a result, the energy density, capacity, and cycle characteristics of the lithium secondary battery 300 are further improved.
- the solid electrolyte 310 is not particularly limited, and examples thereof include those containing a resin and a lithium salt.
- a resin is not particularly limited, but for example, a resin having an ethylene oxide unit in the main chain and / or the side chain, an acrylic resin, a vinyl resin, an ester resin, a nylon resin, a polysiloxane, a polyphosphazene, and a polyvinylidenefro.
- Examples thereof include ride, polymethylmethacrylate, polyamide, polyimide, aramid, polylactic acid, polyethylene, polystyrene, polyurethane, polypropylene, polybutylene, polyacetal, polysulfone, polytetrafluoroethylene and the like.
- the above resins may be used alone or in combination of two or more.
- the lithium salt contained in the solid electrolyte 310 is not particularly limited, and is, for example, LiI, LiCl, LiBr, LiF, LiBF 4 , LiPF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN (SO 2 F) 2 , LiN ( SO 2 CF 3 ) 2 , LiN (SO 2 CF 3 CF 3 ) 2 , LiB (O 2 C 2 H 4 ) 2 , LiB (O 2 C 2 H 4 ) F 2 , LiB (OCOCF 3 ) 4 , LiNO 3 , And Li 2 SO 4 and the like.
- LiI LiI
- LiCl LiBr
- LiF LiBF 4
- LiPF 6 LiAsF 6
- LiSO 3 CF 3 LiN (SO 2 F) 2 , LiN ( SO 2 CF 3 ) 2 , LiN (SO 2 CF 3 CF 3 ) 2 , LiB (O 2 C 2 H 4 ) 2 , LiB (O 2
- the content ratio of the resin and the lithium salt in the solid electrolyte is determined by the ratio of the oxygen atom of the resin to the lithium atom of the lithium salt ([Li] / [O]).
- the content ratio of the resin to the lithium salt is such that the above ratio ([Li] / [O]) is preferably 0.02 or more and 0.20 or less, more preferably 0.03 or more and 0.15.
- the adjustment is made so as to be more preferably 0.04 or more and 0.12 or less.
- the solid electrolyte 310 may contain components other than the above resin and lithium salt. Such components are not particularly limited, and examples thereof include salts other than solvents and lithium salts.
- the salt other than the lithium salt is not particularly limited, and examples thereof include salts of Li, Na, K, Ca, and Mg.
- the solvent is not particularly limited, and examples thereof include those exemplified in the electrolytic solution that can be contained in the lithium secondary battery 100.
- the average thickness of the solid electrolyte 310 is preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, and further preferably 15 ⁇ m or less. According to such an embodiment, the volume occupied by the solid electrolyte 310 in the lithium secondary battery 300 is reduced, so that the energy density of the lithium secondary battery 300 is further improved.
- the average thickness of the solid electrolyte 310 is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, and further preferably 10 ⁇ m or more. According to such an aspect, the positive electrode 120 and the negative electrode 130 can be more reliably isolated, and the short circuit of the battery can be further suppressed.
- solid electrolyte includes a gel electrolyte.
- the gel electrolyte is not particularly limited, and examples thereof include those containing a polymer, an organic solvent, and a lithium salt.
- the polymer in the gel electrolyte is not particularly limited, and examples thereof include a copolymer of polyethylene and / or polyethylene oxide, polyvinylidene fluoride, and a copolymer of polyvinylidene fluoride and hexafluoropropylene.
- a solid electrolyte interface layer may be formed on the surface of the negative electrode 130.
- the SEI layer formed is not particularly limited, but may contain, for example, an inorganic compound containing lithium, an organic compound containing lithium, and the like.
- the typical average thickness of the SEI layer is 1 nm or more and 10 ⁇ m or less.
- the lithium secondary battery 300 can be manufactured in the same manner as the manufacturing method of the lithium secondary battery 100 according to the first embodiment described above, except that a solid electrolyte is used instead of the separator.
- the method for producing the solid electrolyte 310 is not particularly limited as long as it is a method for obtaining the above-mentioned solid electrolyte 310, but for example, it may be as follows.
- a resin conventionally used for the solid electrolyte and a lithium salt (for example, the above-mentioned resin and the lithium salt as the resin that the solid electrolyte 310 can contain) are dissolved in an organic solvent.
- the solid electrolyte 310 is obtained by casting the obtained solution onto a molding substrate so as to have a predetermined thickness.
- the compounding ratio of the resin and the lithium salt may be determined by the ratio ([Li] / [O]) of the oxygen atom of the resin and the lithium atom of the lithium salt, as described above.
- the above ratio ([Li] / [O]) is, for example, 0.02 or more and 0.20 or less.
- the organic solvent is not particularly limited, but acetonitrile may be used, for example.
- the molding substrate is not particularly limited, but for example, a PET film or a glass substrate may be used.
- the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
- the present invention can be modified in various ways as long as it does not deviate from the gist thereof. ..
- the positive electrode 120 may be formed on both sides of the positive electrode current collector 110.
- the lithium secondary battery has two positive electrodes 120, two negative electrodes 130 arranged to face each positive electrode 120, and two separators 140 arranged between each of the positive electrode 120 and the negative electrode 130.
- the solid electrolyte 310 is provided. According to such an aspect, the capacity of the lithium secondary battery can be further improved.
- the lithium secondary battery of this embodiment may be a lithium solid secondary battery. According to such an embodiment, since it is not necessary to use the electrolytic solution, the problem of electrolytic solution leakage does not occur, and the safety of the battery is further improved.
- the lithium secondary battery of the present embodiment may have a current collector arranged so as to be in contact with the negative electrode.
- a current collector is not particularly limited, and examples thereof include a current collector that can be used as a negative electrode material.
- the lithium secondary battery does not have a negative electrode current collector, the negative electrode itself acts as a current collector.
- terminals for connecting to an external circuit may be attached to the positive electrode current collector and the negative electrode.
- metal terminals of 10 ⁇ m or more and 1 mm or less for example, Al, Ni, etc.
- the joining method a conventionally known method may be used, and for example, ultrasonic welding may be used.
- high energy density or “high energy density” means that the total volume of the battery or the capacity per total mass is high, but preferably 800 Wh / L or more or 350 Wh. It is / kg or more, more preferably 900 Wh / L or more or 400 Wh / kg or more, and further preferably 1000 Wh / L or more or 450 Wh / kg or more.
- excellent in cycle characteristics means that the rate of decrease in battery capacity is low before and after the number of charge / discharge cycles that can be expected in normal use. That is, when comparing the first discharge capacity after the initial charge / discharge with the capacity after the charge / discharge cycle of the number of times that can be expected in normal use, the capacity after the charge / discharge cycle is the capacity after the initial charge / discharge. It means that there is almost no decrease with respect to the first discharge capacity of.
- the "number of times that can be assumed in normal use” depends on the application in which the lithium secondary battery is used, but is, for example, 30 times, 50 times, 70 times, 100 times, 300 times, or 500 times. be.
- the capacity after the charge / discharge cycle is hardly reduced with respect to the first discharge capacity after the initial charge / discharge, depending on the application in which the lithium secondary battery is used, for example, charge. It means that the capacity after the discharge cycle is 75% or more, 80% or more, or 85% or more with respect to the first discharge capacity after the initial charge / discharge.
- separator As a separator, a separator having a predetermined size (50 mm ⁇ 50 mm) in which 2 ⁇ m polyvinylidene fluoride (PVDF) was coated on both sides of a 12 ⁇ m polyethylene microporous membrane was prepared.
- PVDF polyvinylidene fluoride
- a mixture of 96 parts by mass of LiNi 0.85 Co 0.12 Mn 0.03 O 2 as the positive electrode active material, 2 parts by mass of carbon black as the conductive auxiliary agent, and 2 parts by mass of polyvinylidene fluoride (PVDF) as the binder is used to collect the positive electrode. It was applied to one side of a 12 ⁇ m Al foil as a body and press-molded. The obtained molded body was punched to a predetermined size (40 mm ⁇ 40 mm) by punching to obtain a positive electrode.
- PVDF polyvinylidene fluoride
- a dimethoxyethane (DME) solution of 4M LiN (SO 2 F) 2 (LFSI) was prepared.
- the positive electrode, the separator, and the negative electrode were laminated in this order to obtain a laminated body.
- the buffer function layer is formed on the separator, the buffer function layer is laminated so as to face the negative electrode, and when the metal layer is formed on the negative electrode, the metal layer is laminated so as to face the separator.
- a 100 ⁇ m Al terminal and a 100 ⁇ m Ni terminal were joined to the positive electrode and the negative electrode by ultrasonic welding, respectively, and then inserted into the outer body of the laminate.
- the above electrolytic solution was injected into the above exterior body.
- a lithium secondary battery was obtained by sealing the exterior body.
- a secondary battery including a positive electrode, a separator, and a negative electrode was prepared by using Cu formed by rolling with an orientation surface of (200) and a maximum surface roughness Rz of 0.3 ⁇ m as a negative electrode.
- a secondary battery including a positive electrode, a separator, and a negative electrode was prepared by using Cu formed by rolling with an orientation surface of (200) and a maximum surface roughness Rz of 0.7 ⁇ m as a negative electrode.
- a secondary battery including a positive electrode, a separator, and a negative electrode was prepared by using Cu formed by rolling with an orientation surface of (220) and a maximum surface roughness Rz of 0.7 ⁇ m as a negative electrode.
- a secondary battery including a positive electrode, a separator, and a negative electrode was prepared by using Cu formed by rolling with an oriented surface of (200) and a maximum surface roughness Rz of 1.0 ⁇ m as a negative electrode.
- a secondary battery provided with a positive electrode, a separator, and a negative electrode was prepared using Cu formed by rolling with an oriented surface of (200) and a maximum surface roughness Rz of 1.2 ⁇ m as the negative electrode.
- the prepared lithium secondary battery was charged at 0.2 mAh / cm 2 until the voltage reached 4.2 V (initial charge), and then discharged at 0.2 mAh / cm 2 until the voltage reached 3.0 V. (Initial discharge).
- a charge / discharge cycle of charging at 1.0 mAh / cm 2 until the voltage reaches 4.2 V and then discharging at 1.0 mAh / cm 2 until the voltage reaches 3.0 V is performed in an environment at a temperature of 25 ° C. Then, 49 cycles were repeated.
- the capacity (initial capacity) obtained from the initial charge was 60 mAh.
- the ratio of the discharge capacity obtained from the discharge in the 50th cycle of the charge / discharge cycle to the discharge capacity obtained from the discharge in the second cycle of the charge / discharge cycle is maintained. It was calculated as a rate (%) and used as an index of cycle characteristics. The higher the capacity retention rate, the better the cycle characteristics. Table 1 shows the capacity retention rate in each example.
- the lithium secondary batteries of Examples 1 to 4 showed a relatively high capacity retention rate of 88% to 90%.
- the capacity retention rate was 70 to 71%. That is, in Examples 1 to 4 in which the orientation plane is the (200) plane or the (220) plane and Cu having a maximum surface roughness Rz of 1.0 ⁇ m or less is used, it is compared with Comparative Examples 1 to 3. It can be seen that the capacity retention rate is high and the cycle characteristics are excellent in comparison.
- the lithium secondary battery of the present invention has a high energy density and excellent cycle characteristics, it has industrial applicability as a power storage device used for various purposes.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
(リチウム2次電池)
図1は、第1の本実施形態に係るリチウム2次電池の概略断面図である。図1に示すように、第1の本実施形態のリチウム2次電池100は、正極120と、負極活物質を有しない負極130と、正極120と負極130との間に配置されているセパレータ140と、を備える。正極120は、セパレータ140に対向する面とは反対側の面に正極集電体110を有する。
負極130は、負極活物質を有しないものである。負極活物質を有する負極を備えるリチウム2次電池は、その負極活物質の存在に起因して、エネルギー密度を高めることが困難である。一方、本実施形態のリチウム2次電池100は負極活物質を有しない負極130を備えるため、そのような問題が生じない。すなわち、本実施形態のリチウム2次電池100は、リチウム金属が負極130の表面に析出し、及び、その析出したリチウム金属が電解溶出することによって充放電が行われるため、エネルギー密度が高い。
正極120は、正極活物質を含むため、リチウム2次電池100は、安定性に優れ、高い出力電圧を有するものとなる。本明細書において、「正極活物質」とは、リチウムイオンを正極120に保持するための物質を意味し、リチウムイオンのホスト物質と換言してもよい。そのような正極活物質としては、特に限定されないが、例えば、金属酸化物及び金属リン酸塩が挙げられる。上記金属酸化物としては、特に限定されないが、例えば、酸化コバルト系化合物、酸化マンガン系化合物、及び酸化ニッケル系化合物等が挙げられる。上記金属リン酸塩としては、特に限定されないが、例えば、リン酸鉄系化合物、及びリン酸コバルト系化合物が挙げられる。典型的な正極活物質としては、LiCoO2、LiNixCoyMnzO(x+y+z=1)、LiNixMnyO(x+y=1)、LiNiO2、LiMn2O4、LiFePO、LiCoPO、LiFeOF、LiNiOF、及びTiS2が挙げられる。上記のような正極活物質は、1種を単独で又は2種以上を併用して用いられる。
正極120の片側には、正極集電体110が形成されている。正極集電体110は、電池においてリチウムイオンと反応しない導電体であれば特に限定されない。そのような正極集電体としては、例えば、アルミニウムが挙げられる。
セパレータ140は、正極120と負極130とを隔離することにより電池が短絡することを防ぎつつ、正極120と負極130との間の電荷キャリアとなるリチウムイオンのイオン伝導性を確保するための部材であり、電子導電性を有さず、リチウムイオンと反応しない材料により構成される。また、セパレータ140は当該電解液を保持する役割も担う。セパレータ140は、上記役割を担う限りにおいて限定はないが、例えば、多孔質のポリエチレン(PE)、ポリプロピレン(PP)、又はこれらの積層構造により構成される。
リチウム2次電池100は、電解液を有していてもよい。電解液は、セパレータ140に浸潤させてもよく、リチウム2次電池100と共に電解液を封入したものを完成品としてもよい。電解液は、電解質及び溶媒を含有し、イオン伝導性を有する溶液であり、リチウムイオンの導電経路として作用する。このため、電解液を有するリチウム2次電池100は、内部抵抗が一層低下し、エネルギー密度、容量、及びサイクル特性が一層向上する。
図2に本実施形態のリチウム2次電池の1つの使用態様を示す。リチウム2次電池100は、正極集電体110及び負極130に、リチウム2次電池100を外部回路に接続するための正極端子220及び負極端子230がそれぞれ接合されている。リチウム2次電池100は、負極端子230を外部回路の一端に、正極端子220を外部回路のもう一端に接続することにより充放電される。
図1に示すようなリチウム2次電池100の製造方法としては、上述の構成を備えるリチウム2次電池を製造することができる方法であれば特に限定されないが、例えば以下のような方法が挙げられる。
(リチウム2次電池)
一般に、液体電解質を備える電池は、液体の揺らぎに起因して、電解質から負極表面に対してかかる物理的圧力が場所によって異なる傾向にある。一方、リチウム2次電池300は、固体電解質310を備えるため、固体電解質310から負極130表面にかかる圧力が一層均一なものとなり、負極130の表面に析出するキャリア金属の形状を一層均一化することができる。すなわち、このような態様によれば、負極130の表面に析出するキャリア金属が、デンドライト状に成長することが一層抑制されるため、リチウム2次電池300のサイクル特性は一層優れたものとなる。
リチウム2次電池300は、セパレータに代えて固体電解質を用いること以外は、上述した第1の本実施形態に係るリチウム2次電池100の製造方法と同様にして、製造することができる。
リチウム2次電池の製造に関する各工程は以下のように実施した。
以下のそれぞれの実施例に合わせて準備した10μmのCu箔を負極として用いる。負極に対しては防錆処理などを施す。
セパレータとして、12μmのポリエチレン微多孔膜の両面に2μmのポリビニリデンフロライド(PVDF)がコーティングされた所定の大きさ(50mm×50mm)のセパレータを準備した。
正極活物質としてLiNi0.85Co0.12Mn0.03O2を96質量部、導電助剤としてカーボンブラックを2質量部、及びバインダーとしてポリビニリデンフロライド(PVDF)を2質量部混合したものを、正極集電体としての12μmのAl箔の片面に塗布し、プレス成型した。得られた成型体を、打ち抜き加工により、所定の大きさ(40mm×40mm)に打ち抜き、正極を得た。
電解液として、4M LiN(SO2F)2(LFSI)のジメトキシエタン(DME)溶液を準備した。次いで、正極、セパレータ、及び負極を、この順に積層することで積層体を得た。なお、セパレータに緩衝機能層が形成されている場合は、緩衝機能層が負極と対向するようにして、負極に金属層が形成されている場合は、金属層がセパレータと対向するようにして積層を実施した。更に、正極及び負極に、それぞれ100μmのAl端子及び100μmのNi端子を超音波溶接で接合した後、ラミネートの外装体に挿入した。次いで、上記の電解液を上記の外装体に注入した。外装体を封止することにより、リチウム2次電池を得た。
圧延により形成された、配向面が(200)面、表面粗さの最大高さRzを0.3μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
圧延により形成された、配向面が(200)面、表面粗さの最大高さRzを0.7μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
圧延により形成された、配向面が(220)面、表面粗さの最大高さRzを0.7μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
圧延により形成された、配向面が(200)面、表面粗さの最大高さRzを1.0μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
圧延により形成された、配向面が(200)面、表面粗さの最大高さRzを1.2μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
電気めっきにより形成された電解銅箔であって、配向面が(111)面、表面粗さの最大高さRzを0.8μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
電気めっきにより形成された電解銅箔であって、配向面が(111)面、表面粗さの最大高さRzを1.5μmとしたCuを負極として用い、正極、セパレータ、及び負極を備える2次電池を作成した。
以下のようにして、各実施例及び比較例で作製したリチウム2次電池のサイクル特性を評価した。
Claims (5)
- 正極と、負極活物質を有しない負極と、を備えるリチウム2次電池であって、
前記負極は、表面粗さの最大高さRzが1.0μm以下であり、かつ配向面が(200)面または(220)面のCuである、
リチウム2次電池。 - 前記Cuが圧延により形成される、
請求項1に記載のリチウム2次電池。 - リチウム金属が前記負極の表面に析出し、かつ析出した前記リチウム金属が溶解することによって充放電が行われる、
請求項1または請求項2に記載のリチウム2次電池。 - 初期充電の前に、前記負極の表面にリチウム箔が形成されていない、
請求項1から3のいずれか1項に記載のリチウム2次電池。 - エネルギー密度が350Wh/kg以上である、
請求項1から請求項4のいずれか1項に記載のリチウム2次電池。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022558804A JPWO2022091407A1 (ja) | 2020-11-02 | 2020-11-02 | |
CN202080106741.1A CN116569355A (zh) | 2020-11-02 | 2020-11-02 | 锂二次电池 |
KR1020237018417A KR20230104654A (ko) | 2020-11-02 | 2020-11-02 | 리튬 이차 전지 |
EP20959922.4A EP4239715A1 (en) | 2020-11-02 | 2020-11-02 | Lithium secondary battery |
PCT/JP2020/041040 WO2022091407A1 (ja) | 2020-11-02 | 2020-11-02 | リチウム2次電池 |
US18/141,094 US20230268625A1 (en) | 2020-11-02 | 2023-04-28 | Lithium secondary battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2020/041040 WO2022091407A1 (ja) | 2020-11-02 | 2020-11-02 | リチウム2次電池 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/141,094 Continuation US20230268625A1 (en) | 2020-11-02 | 2023-04-28 | Lithium secondary battery |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022091407A1 true WO2022091407A1 (ja) | 2022-05-05 |
Family
ID=81382187
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/041040 WO2022091407A1 (ja) | 2020-11-02 | 2020-11-02 | リチウム2次電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20230268625A1 (ja) |
EP (1) | EP4239715A1 (ja) |
JP (1) | JPWO2022091407A1 (ja) |
KR (1) | KR20230104654A (ja) |
CN (1) | CN116569355A (ja) |
WO (1) | WO2022091407A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009004370A (ja) * | 2007-05-23 | 2009-01-08 | Sony Corp | 集電体、負極および二次電池 |
WO2015145288A1 (ja) * | 2014-03-24 | 2015-10-01 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
JP2019501480A (ja) * | 2015-11-18 | 2019-01-17 | シェンチェン・インスティテューツ・オブ・アドバンスド・テクノロジー・チャイニーズ・アカデミー・オブ・サイエンシーズShenzhen Institutes Of Advanced Technology Chinese Academy Of Sciences | 二次電池及びその製造方法 |
WO2020158181A1 (ja) * | 2019-01-31 | 2020-08-06 | パナソニックIpマネジメント株式会社 | リチウム金属二次電池 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019517722A (ja) | 2016-06-08 | 2019-06-24 | ソリッドエナジー システムズ,エルエルシー | 高エネルギー密度、高出力密度、高容量及び室温対応「アノードフリー」二次電池 |
KR102115602B1 (ko) | 2017-06-21 | 2020-05-26 | 주식회사 엘지화학 | 리튬 이차전지 |
-
2020
- 2020-11-02 CN CN202080106741.1A patent/CN116569355A/zh active Pending
- 2020-11-02 EP EP20959922.4A patent/EP4239715A1/en active Pending
- 2020-11-02 WO PCT/JP2020/041040 patent/WO2022091407A1/ja active Application Filing
- 2020-11-02 KR KR1020237018417A patent/KR20230104654A/ko unknown
- 2020-11-02 JP JP2022558804A patent/JPWO2022091407A1/ja active Pending
-
2023
- 2023-04-28 US US18/141,094 patent/US20230268625A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009004370A (ja) * | 2007-05-23 | 2009-01-08 | Sony Corp | 集電体、負極および二次電池 |
WO2015145288A1 (ja) * | 2014-03-24 | 2015-10-01 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池 |
JP2019501480A (ja) * | 2015-11-18 | 2019-01-17 | シェンチェン・インスティテューツ・オブ・アドバンスド・テクノロジー・チャイニーズ・アカデミー・オブ・サイエンシーズShenzhen Institutes Of Advanced Technology Chinese Academy Of Sciences | 二次電池及びその製造方法 |
WO2020158181A1 (ja) * | 2019-01-31 | 2020-08-06 | パナソニックIpマネジメント株式会社 | リチウム金属二次電池 |
Also Published As
Publication number | Publication date |
---|---|
CN116569355A (zh) | 2023-08-08 |
KR20230104654A (ko) | 2023-07-10 |
EP4239715A1 (en) | 2023-09-06 |
JPWO2022091407A1 (ja) | 2022-05-05 |
US20230268625A1 (en) | 2023-08-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108292779B (zh) | 锂离子二次电池 | |
US20090123851A1 (en) | Positive-electrode active material for lithium-ion secondary battery, positive electrode, manufacturing method thereof, and lithium-ion secondary battery | |
WO2022038793A1 (ja) | リチウム2次電池 | |
CN111095618B (zh) | 蓄电装置用电极和其制造方法 | |
JP2009043477A (ja) | 正極活物質、これを用いた正極および非水電解質電池 | |
WO2021250803A1 (ja) | 2次電池及びその製造方法 | |
WO2015083262A1 (ja) | リチウムイオン二次電池用負極材料及びその製造方法、リチウムイオン二次電池用負極及びその製造方法並びにリチウムイオン二次電池 | |
WO2022054343A1 (ja) | リチウム2次電池 | |
CN111095617A (zh) | 锂离子二次电池用负极和包含所述负极的锂离子二次电池 | |
WO2022054279A1 (ja) | リチウム2次電池 | |
JP4582684B2 (ja) | 非水二次電池 | |
WO2021192260A1 (ja) | 固体電池の製造方法及び固体電池 | |
WO2022091407A1 (ja) | リチウム2次電池 | |
JP2003208925A (ja) | 二次電源 | |
US20230137413A1 (en) | Lithium secondary battery and method for using same | |
WO2021245745A1 (ja) | 電池及びその製造方法 | |
WO2022137346A1 (ja) | 電池システム、充電装置及び充電方法 | |
WO2022215160A1 (ja) | リチウム2次電池 | |
JP7340303B2 (ja) | リチウム2次電池及びその製造方法 | |
WO2022070326A1 (ja) | リチウム2次電池、及びアノードフリー電池 | |
WO2021229635A1 (ja) | リチウム2次電池 | |
WO2021229680A1 (ja) | 電池及びその製造方法 | |
WO2022102072A1 (ja) | リチウム2次電池 | |
WO2022244110A1 (ja) | リチウム2次電池及びその使用方法、並びにリチウム2次電池の製造方法 | |
WO2023002537A1 (ja) | リチウム2次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20959922 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022558804 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202080106741.1 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 20237018417 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2020959922 Country of ref document: EP Effective date: 20230602 |