JP2022546292A - フリースタンディングフィルム型リチウム二次電池用正極材、この製造方法及びこれを含むリチウム二次電池 - Google Patents
フリースタンディングフィルム型リチウム二次電池用正極材、この製造方法及びこれを含むリチウム二次電池 Download PDFInfo
- Publication number
- JP2022546292A JP2022546292A JP2022511087A JP2022511087A JP2022546292A JP 2022546292 A JP2022546292 A JP 2022546292A JP 2022511087 A JP2022511087 A JP 2022511087A JP 2022511087 A JP2022511087 A JP 2022511087A JP 2022546292 A JP2022546292 A JP 2022546292A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- sulfur
- carbon
- secondary battery
- lithium secondary
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 110
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 110
- 239000011593 sulfur Substances 0.000 claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000007774 positive electrode material Substances 0.000 claims abstract description 73
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000011068 loading method Methods 0.000 claims abstract description 7
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 36
- 239000002041 carbon nanotube Substances 0.000 claims description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 29
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical group [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002134 carbon nanofiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000006231 channel black Substances 0.000 claims description 2
- 239000006232 furnace black Substances 0.000 claims description 2
- 239000006233 lamp black Substances 0.000 claims description 2
- 239000002121 nanofiber Substances 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 239000006234 thermal black Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 31
- 238000001035 drying Methods 0.000 abstract description 21
- 230000000052 comparative effect Effects 0.000 description 32
- 239000010408 film Substances 0.000 description 26
- 239000004020 conductor Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 12
- -1 etc. Chemical compound 0.000 description 9
- 239000007773 negative electrode material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000005463 sulfonylimide group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 229910005143 FSO2 Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010090 LiAlO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910016622 LixFe2O3 Inorganic materials 0.000 description 1
- 229910015103 LixWO2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910000417 bismuth pentoxide Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 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
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M2004/028—Positive electrodes
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
(S2)上記(S1)段階で形成された混合物を熱処理する段階;及び
(S3)上記(S2)段階で形成された硫黄‐炭素複合体を容器に充填した後、加圧して炭素を含む硫黄溶融物を形成する段階;を含むリチウム二次電池用正極材の製造方法を提供する。
本発明はフリースタンディングフィルム形態のリチウム二次電池用正極材であって、上記正極材は炭素を含む硫黄溶融物を含むものであってもよい。上記正極材は硫黄溶融物に多孔性炭素材が分散された形態であってもよい。また、上記正極材は後述するように、硫黄と多孔性炭素材のみを原料にして乾式工程で製造されたもので、もっぱら硫黄と多孔性炭素材のみで構成されたものであってもよい。
図1は、リチウム二次電池用正極材で使用されることができる硫黄、炭素及び硫黄‐炭素複合体を加圧する場合の物性変化及び成形性を示す模式図である。
(S1)硫黄と多孔性炭素材を混合する段階;
(S2)上記(S1)段階で形成された混合物を熱処理する段階;及び
(S3)上記(S2)段階で形成された硫黄‐炭素複合体を容器に充填した後、加圧して炭素を含む硫黄溶融物を形成する段階。
本発明はまた、上記のような炭素を含む硫黄溶融物を含むフリースタンディングフィルム型正極材を正極で含むリチウム二次電池に関する。
硫黄(S)と炭素ナノチューブ(CNT)を固体状態で65:35の質量比で均一に混合した後、100rpmの条件で1時間ボールミーリングして混合物を製造した。
(1)フリースタンディングフィルム型正極材の製造
上記製造例1の硫黄‐炭素複合体(S‐CNT)をモールドに充填させた後、油圧プレスを利用して1MPaの圧力で加圧することで炭素を含む硫黄溶融物を形成して、図2に示すようにフリースタンディングフィルム型正極材を製造した。
上記製造されたフリースタンディングフィルム型正極材を正極で用意し、厚さ150μmのリチウム金属を負極で用意した。
上記硫黄‐炭素複合体の加圧時の圧力を1.5Mpaにしたことを除いて実施例1と同様の方法で実施した。
上記硫黄‐炭素複合体の加圧時の圧力を3Mpaにしたことを除いて実施例1と同様の方法で実施した。
上記製造例1の硫黄‐炭素複合体(S‐CNT)、導電材及びバインダーを90:5:5の質量比で混合してスラリーを製造した後、アルミニウムホイルの上にコーティングした後、乾燥及び圧延して正極を製造したことを除いて実施例1と同様の方法でリチウム‐硫黄二次電池を製造した。この時、上記導電材はVGCF(Vapor grown carbon fiber)を使用し、上記バインダーはSBR(Styrene Butadiene Rubber)を使用した。
圧延された厚さを比較例1に比べて相対的に減少させ、正極の気孔率が65%になるようにしたことを除いて比較例1と同様の方法でリチウム‐硫黄二次電池を製造した。
圧延された厚さを比較例2に比べて相対的に減少させ、正極の気孔率が58%になるようにしたことを除いて比較例1と同様の方法でリチウム‐硫黄二次電池を製造した。
加圧時の圧力を0.5Mpaにしたことを除いて実施例1と同様の方法で実施した。
加圧時の圧力を20Mpaにしたことを除いて実施例1と同様の方法でリチウム‐硫黄二次電池を製造した。
硫黄‐炭素複合体と一緒に導電材であるCNTを10質量%のモールドに充填して加圧したことを除いて、実施例1と同様の方法でリチウム‐硫黄二次電池を製造した。この時、導電材の含量は硫黄‐炭素複合体と導電材の全体質量を基準にしたものである。
実施例及び比較例で正極材を製造するために工程に要される時間を測定して比べた。工程に必要な時間は下記表1に記載したとおりである。
実施例及び比較例でそれぞれ製造された正極の気孔率を測定して比べ、その結果は表2に記載したとおりである。
実施例及び比較例で製作された電池に対して25℃で0.1C放電、0.1C充電して容量(Capacity、mAh)を測定し、充放電を繰り返して測定することで容量及び充電効率を測定し、その結果を下記表3及び図4aないし図4eに示す。上記表2に示すように、比較例4は加圧圧力が低くて硫黄‐炭素複合体の間の結集力が不足して電極が製造されなかったので、実施例1ないし3と比較例1ないし3及び5と6に対して実験を行った。
製造例1で原料として使われた炭素ナノチューブ(CNT)と硫黄‐炭素複合体(S‐CNT)を加圧工程に適用した後、内部形態を確認した。加圧工程は実施例1の(1)に示すように適用した。
Claims (12)
- フリースタンディングフィルム形態のリチウム二次電池用正極材であって、
上記正極材は炭素を含む硫黄溶融物を含むものである、リチウム二次電池用正極材。 - 上記炭素を含む硫黄溶融物は、上記硫黄溶融物の内部に多孔性炭素材が分散された形態である、請求項1に記載のリチウム二次電池用正極材。
- 上記炭素を含む硫黄溶融物は、硫黄50質量%ないし80質量%及び多孔性炭素材20質量%ないし50質量%で構成されたものである、請求項1に記載のリチウム二次電池用正極材。
- 上記正極材内部の接着力は10gf/cm以上である、請求項1に記載のリチウム二次電池用正極材。
- 上記多孔性炭素材は、グラファイト(graphite);グラフェン(graphene);デンカブラック、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック及びサーマルブラックの中で選択されるカーボンブラック;単一壁炭素ナノチューブ(SWCNT)及び多重壁炭素ナノチューブ(MWCNT)が選択される炭素ナノチューブ(CNT);グラファイトナノファイバー(GNF)、カーボンナノファイバー(CNF)及び活性化炭素ファイバー(ACF)の中で選択される炭素繊維;及び活性炭素からなる群から選択される1種以上を含むものである、請求項2に記載のリチウム二次電池用正極材。
- 上記正極材の気孔率は68%以下である、請求項1に記載のリチウム二次電池用正極材。
- (S1)硫黄と多孔性炭素材を混合する段階;
(S2)上記(S1)段階で形成された混合物を熱処理する段階;及び
(S3)上記(S2)段階で形成された硫黄‐炭素複合体を容器に充填した後、加圧して炭素を含む硫黄溶融物を形成する段階;を含むリチウム二次電池用正極材の製造方法。 - 上記熱処理は130℃ないし170℃で行われる、請求項7に記載のリチウム二次電池用正極材の製造方法。
- 上記加圧は0.8MPaないし15MPaの圧力下で行われる、請求項7に記載のリチウム二次電池用正極材の製造方法。
- 請求項1ないし請求項6のいずれか1項に記載の正極材を含む正極;
リチウム金属またはリチウム合金を含む負極;
上記正極と負極の間に位置する分離膜;及び
上記正極、負極及び分離膜が含浸された電解液;
を含むリチウム二次電池。 - 上記リチウム二次電池はリチウム‐硫黄二次電池である、請求項10に記載のリチウム二次電池。
- 上記正極のローディング量は3.0mAh/cm2ないし5.0mAh/cm2である、請求項10に記載のリチウム二次電池。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20200063882 | 2020-05-27 | ||
KR10-2020-0063882 | 2020-05-27 | ||
KR1020210064083A KR20210146800A (ko) | 2020-05-27 | 2021-05-18 | 프리스탠딩 필름형 리튬 이차전지용 양극재, 이의 제조방법 및 이를 포함하는 리튬 이차전지 |
KR10-2021-0064083 | 2021-05-18 | ||
PCT/KR2021/006415 WO2021241959A1 (ko) | 2020-05-27 | 2021-05-24 | 프리스탠딩 필름형 리튬 이차전지용 양극재, 이의 제조방법 및 이를 포함하는 리튬 이차전지 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2022546292A true JP2022546292A (ja) | 2022-11-04 |
JP7431947B2 JP7431947B2 (ja) | 2024-02-15 |
Family
ID=78744694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022511087A Active JP7431947B2 (ja) | 2020-05-27 | 2021-05-24 | フリースタンディングフィルム型リチウム二次電池用正極材、この製造方法及びこれを含むリチウム二次電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20220359861A1 (ja) |
EP (1) | EP4002516A4 (ja) |
JP (1) | JP7431947B2 (ja) |
CN (1) | CN114207875A (ja) |
WO (1) | WO2021241959A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114792813B (zh) * | 2022-04-27 | 2023-07-14 | 电子科技大学 | 锂-二氧化碳电池无碳自支撑正极膜材料的制备及电池 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160051610A (ko) * | 2014-10-31 | 2016-05-11 | 주식회사 엘지화학 | 프리스탠딩 필름형 리튬-설퍼 전지용 양극재 및 이를 포함하는 리튬-설퍼 전지 |
US20180212252A1 (en) * | 2017-01-26 | 2018-07-26 | Caitlin Nicole Dillard | Rapid sulfur melt diffusion into carbon host for making electrodes |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20050052258A (ko) * | 2003-11-29 | 2005-06-02 | 삼성에스디아이 주식회사 | 리튬 설퍼 전지 및 그 제조방법 |
KR101384198B1 (ko) * | 2011-05-31 | 2014-04-25 | 한양대학교 산학협력단 | 카본 황 복합체의 제조 방법, 이에 의하여 제조된 카본 황 복합체 및 이를 포함하는 리튬황 전지 |
US20180100037A1 (en) * | 2015-07-13 | 2018-04-12 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Copolymerization of elemental sulfur and epoxy functional styrenics |
KR101669316B1 (ko) * | 2013-07-30 | 2016-10-25 | 주식회사 엘지화학 | 황-탄소 복합체 및 그의 제조방법 |
KR101683963B1 (ko) * | 2014-05-26 | 2016-12-07 | 현대자동차주식회사 | 이중 건식 복합화를 통한 황-탄소 복합체 제조 방법 |
CN109873120A (zh) | 2017-12-05 | 2019-06-11 | 中国科学院大连化学物理研究所 | 无金属集流体、自支撑石墨烯基锂硫电池正极的制备方法 |
KR102268184B1 (ko) * | 2018-08-08 | 2021-06-22 | 주식회사 엘지화학 | 황-탄소 복합체, 이의 제조방법, 이를 포함하는 양극 및 리튬 이차전지 |
US20200052279A1 (en) * | 2018-08-13 | 2020-02-13 | Tuqiang Chen | Method of preparing energy storage electrodes |
KR102150848B1 (ko) | 2018-11-28 | 2020-09-02 | 주식회사 보아스에스이 | 신재생에너지 발전시스템 고장 감지방법 |
KR102081775B1 (ko) | 2019-08-22 | 2020-02-26 | 주식회사 엘지화학 | 탄소계 2차 입자를 포함하는 리튬-황 전지용 양극, 이의 제조방법 및 이를 포함하는 리튬-황 전지 |
US11454837B2 (en) | 2019-11-22 | 2022-09-27 | Eagle Technology, Llc | AOM system with interface board and signal vias and related methods |
-
2021
- 2021-05-24 CN CN202180004710.XA patent/CN114207875A/zh active Pending
- 2021-05-24 JP JP2022511087A patent/JP7431947B2/ja active Active
- 2021-05-24 US US17/634,114 patent/US20220359861A1/en active Pending
- 2021-05-24 WO PCT/KR2021/006415 patent/WO2021241959A1/ko unknown
- 2021-05-24 EP EP21812418.8A patent/EP4002516A4/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20160051610A (ko) * | 2014-10-31 | 2016-05-11 | 주식회사 엘지화학 | 프리스탠딩 필름형 리튬-설퍼 전지용 양극재 및 이를 포함하는 리튬-설퍼 전지 |
US20180212252A1 (en) * | 2017-01-26 | 2018-07-26 | Caitlin Nicole Dillard | Rapid sulfur melt diffusion into carbon host for making electrodes |
Also Published As
Publication number | Publication date |
---|---|
JP7431947B2 (ja) | 2024-02-15 |
EP4002516A1 (en) | 2022-05-25 |
US20220359861A1 (en) | 2022-11-10 |
WO2021241959A1 (ko) | 2021-12-02 |
EP4002516A4 (en) | 2022-11-09 |
CN114207875A (zh) | 2022-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102006727B1 (ko) | 황-탄소 복합체 및 이를 포함하는 리튬-황 전지 | |
KR101774683B1 (ko) | 전극 활물질 슬러리, 이의 제조 방법 및 이를 포함하는 전고체 이차전지 | |
CN107925042B (zh) | 具有包含聚多巴胺的复合涂层的锂硫电池隔膜、其制造方法及包含其的锂硫电池 | |
US20200067128A1 (en) | Hybrid and solid-state battery architectures with high loading and methods of manufacture thereof | |
CN108140810A (zh) | 二次电池用负极 | |
JP2010205609A (ja) | 電極およびこれを用いた電池 | |
KR20080023373A (ko) | 점토 광물을 포함하고 있는 전극 합제 및 이를 사용한전기화학 셀 | |
WO2020041767A1 (en) | Hybrid and solid-state battery architectures with high loading and methods of manufacture thereof | |
KR102268184B1 (ko) | 황-탄소 복합체, 이의 제조방법, 이를 포함하는 양극 및 리튬 이차전지 | |
JP6573254B2 (ja) | 非水電解質二次電池用負極の製造方法 | |
KR20200056039A (ko) | 흑연을 포함하지 않는 전고체 전지용 복합 음극 및 이의 제조방법 | |
JP2002117851A (ja) | 炭素材料、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 | |
TWI785058B (zh) | 硫-碳材料複合體、鋰硫二次電池用正極材料及鋰硫二次電池 | |
US11394054B2 (en) | Polymer microspheres as binders for composite electrolytes | |
KR101586536B1 (ko) | 전고상 리튬이차전지용 탄소섬유 시트 집전체의 제조방법 및 탄소섬유 시트 집전체를 포함하는 전고상 리튬이차전지 | |
KR20210146800A (ko) | 프리스탠딩 필름형 리튬 이차전지용 양극재, 이의 제조방법 및 이를 포함하는 리튬 이차전지 | |
JP7118138B2 (ja) | リチウム-硫黄電池用分離膜及びこれを含むリチウム-硫黄電池 | |
JP5515257B2 (ja) | 双極型二次電池 | |
JP6212305B2 (ja) | 複合集電体、およびそれを用いた電極と二次電池 | |
JP7431947B2 (ja) | フリースタンディングフィルム型リチウム二次電池用正極材、この製造方法及びこれを含むリチウム二次電池 | |
JP5711825B2 (ja) | 一体型電極アセンブリ及び、該一体型電極アセンブリを用いた二次電池 | |
KR20200137189A (ko) | 음극 및 상기 음극을 포함하는 이차 전지 | |
JP7039846B2 (ja) | 非水電解質二次電池の製造方法 | |
Banitaba | Application of electrospun fibers for the fabrication of high performance all-solid-state fibrous batteries | |
JP2022550821A (ja) | 穴あけされた集電体を含むリチウム二次電池用電極、その製造方法及び前記電極を含むリチウム二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220218 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230216 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230403 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230628 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230807 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231101 |
|
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: 20240122 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240202 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7431947 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |