JP6759189B2 - 電極活物質としてのカプセル化硫黄サブミクロン粒子 - Google Patents
電極活物質としてのカプセル化硫黄サブミクロン粒子 Download PDFInfo
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- JP6759189B2 JP6759189B2 JP2017514823A JP2017514823A JP6759189B2 JP 6759189 B2 JP6759189 B2 JP 6759189B2 JP 2017514823 A JP2017514823 A JP 2017514823A JP 2017514823 A JP2017514823 A JP 2017514823A JP 6759189 B2 JP6759189 B2 JP 6759189B2
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- sulfur
- cathode
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- lithium
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 142
- 229910052717 sulfur Inorganic materials 0.000 title claims description 128
- 239000011593 sulfur Substances 0.000 title claims description 128
- 239000002245 particle Substances 0.000 title claims description 77
- 239000007772 electrode material Substances 0.000 title description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 27
- 229920001940 conductive polymer Polymers 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 239000011258 core-shell material Substances 0.000 claims description 19
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 13
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 11
- 239000003273 ketjen black Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 5
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 5
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 229920000144 PEDOT:PSS Polymers 0.000 description 27
- 229920001021 polysulfide Polymers 0.000 description 25
- 239000005077 polysulfide Substances 0.000 description 25
- 150000008117 polysulfides Polymers 0.000 description 25
- 239000002131 composite material Substances 0.000 description 23
- 229910052799 carbon Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 239000006229 carbon black Substances 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 239000011257 shell material Substances 0.000 description 10
- -1 alkali metal alkoxides Chemical class 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000006182 cathode active material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011533 mixed conductor Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
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- 150000001768 cations Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
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- 239000010419 fine particle Substances 0.000 description 3
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
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- 229920001690 polydopamine Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 150000002118 epoxides Chemical class 0.000 description 1
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- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000011796 hollow space material Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical class [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000034153 membrane organization Effects 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
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
- H01M4/366—Composites as layered products
-
- 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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
Description
発明の分野
本発明は、電極活物質としての利用に適する新規カプセル化サブミクロン硫黄粒子に関する。特に、本発明は、親水性/疎水性混合コポリマーの存在下で形成されるサブミクロン硫黄粒子に関する。結果として生じるカプセル化硫黄サブミクロンコア粒子は、連続するどの層も前の層に対して反対の電荷を有している自己組織化導電性ポリマー層の層の膜によって被覆されている。また、本発明は、膜で被覆されたカプセル化硫黄サブミクロン粒子を含有するカソード、および当該カソードを含む電気化学セルまたは電池に関する。さらに、本発明は、膜被覆炭素−硫黄複合カソードを含むリチウム硫黄電池に関する。
燃焼機関に取って代わる車両エネルギー動力源を開発する継続的な取り組みにおいて、1つの開発分野はプラグイン電気車両であった。今日までその取り組みの多くはそのような車両のための動力源としてのリチウムイオン電池に対して向けられてきた。しかし、主流となって、コストおよび駆動範囲の見地から燃焼機関に匹敵するためには、リチウムイオン電池のエネルギー密度を著しく改善することが必要である。リチウムイオン研究後の至高の目標は、硫黄または酸素など大きな容積を有する変換カソードを純金属アノードと組み合わせて利用することによってエネルギー密度を増大させることである。カソード活物質として、硫黄元素は、遷移金属の酸化物またはリン酸塩に基づく従来使用の材料に比べて5倍大きい容量を提供できる。
Skotheimら(US2014/0205912)は、多重層被覆構造によって保護されたリチウムアノードを有するリチウム電池について記載している。多重層構造の各々のフィルムは、リチウムイオンの通過を可能にするが、リチウム金属表面へのその他のセル成分の到達に対する障壁として働く。多重被覆アノードを含む電気化学セルおよび電池が記載されており、カソードは硫黄元素と導電性炭素材料と結着剤との混合物で構成されている。導電性ポリマー材料は、可能な炭素構成要素として開示されている。しかしながら当該材料は、実施例7に示されているように、混合またはブレンドされて電極基材に塗布されている。カソード活性成分としての、導電性ポリマー多重層系の中にカプセル化されたサブミクロン硫黄粒子は、開示も示唆もされていない。
これらおよびその他の目的は本発明に従って達成され、その第1の実施形態は、コア−シェルサブミクロン粒子であって:
硫黄元素を含むコアと;
硫黄コアの最も近くにある、少なくとも1つの疎水性領域を有するイオン的に帯電した自己組織化導電性コポリマーの第1層;および
第1層に隣接およびイオン結合し、第1層とは相反する電荷を有する、少なくとも第2の導電性ポリマー層;を含む、シェルと
を含み、
場合によって、コアおよび外層のうちの少なくとも1つが官能基化カーボンブラックを含む、コア−シェルサブミクロン粒子を提供する。
先の段落は、一般的な序論として提供されたものであり、以下の特許請求の範囲を限定することを意図するものではない。添付の図面と併せて以下の詳細な説明を参照することによって、本発明の好ましい実施形態がさらなる利点と共に最も良く理解されるであろう。
本記載の全体を通して、記載されている全ての範囲には、特に明記しない限り、全ての値および、その中の部分範囲が含まれる。さらに、不定冠詞「a」または「an」は、特に明記しない限り、「1つ以上」の意味を有する。本発明によれば、用語「車両」は、自動車、トラック バン、バス、ゴルフカートおよびその他の輸送利用形態を含めた輸送のために設計された、いかなる動力によって駆動される装置をも意味する。
硫黄元素を含むコアと;
硫黄コアの最も近くにある、少なくとも1つの疎水性領域を有するイオン的に帯電した自己組織化導電性コポリマーの第1層;および
第1層に隣接およびイオン結合し、第1層とは相反する電荷を有する、少なくとも第2の導電性ポリマー層;を含む、シェルと
を含み、場合によって、コアおよび外層表面のうちの少なくとも1つが官能基化導電性炭素材料を含む、コア−シェルサブミクロン粒子を提供する。
導電等級のPEDOT:PSS(アルドリッチ)の存在下で硫黄粒子を図1に示す化学反応に従って生成させた。薄いPEDOT:PSSシェルの内部に直径1マイクロメートル未満の硫黄粒子が得られた(図2)。硫黄含有量の非常に高い(>95%)硫黄材料が得られた。
図6に描かれているように、導電等級のPEDOT:PSS(アルドリッチ)の存在下でサブミクロン硫黄粒子を調製した。得られた硫黄粒子は直径が1マイクロメートル未満であり、薄いPEDOT:PSSシェルの内部にカプセル化されていた。PEDOT:PSSは全体として負の電荷を有するため、正に帯電したポリ(ジメチルジアリルアンモニウムクロリド)(PDADMAC)の層がPEDOT:PSSシェル上に吸着された。計7層が得られるまで、交互のPEDOT:PSSシェル/PDADMAC皮膜の適用を繰り返した。その後、COOHで官能基化されたケッチェンブラック600JDを硫黄/ポリマー球状物の外面に最小量でかつ密接な接触で適用させた(図6および図7)。こうして、非常に高い硫黄含有量(>95%)を有する硫黄材料が得られた。図7は、7層のPEDOT:PSS/PDADMACによってカプセル化され、かつ官能基化ケッチェンブラック600JD炭素によって部分的に覆われた、得られたサブミクロン硫黄粒子のSEM画像を示す。
図10に示すように、導電等級のPEDOT:PSS(アルドリッチ)の存在下、−COOHで官能基化されたケッチェンブラック600JDを含有する反応混合物中で、サブミクロン硫黄粒子を調製した。官能基化炭素を含有する得られた硫黄粒子は、直径が1マイクロメートル未満であり、薄いPEDOT:PSSシェルの内部にカプセル化されていた。PEDOT:PSSは全体として負の電荷を有するため、正に帯電したポリ(ジメチルジアリルアンモニウムクロリド)(PDADMAC)の層がPEDOT:PSSシェル上に吸着された。計7層が得られるまで、交互のPEDOT:PSSシェル/PDADMAC皮膜の適用を繰り返した。その後、COOHで官能基化されたケッチェンブラック600JDを硫黄/ポリマー球状物の外面に最小量でかつ密接な接触で適用させた(図10)。こうして、非常に高い硫黄含有量(>95%)を有する高導電性硫黄材料が得られた。図11AおよびBは、7層のPEDOT:PSS/PDADMACによってカプセル化され、かつ官能基化ケッチェンブラック600JD炭素によって部分的に覆われた、得られた単一のサブミクロン硫黄粒子のSEM画像およびTEM画像を示す。図11Cは、これらの粒子の凝集物を示す。
ポリ(ジアリルジメチルアンモニウムクロリド)(PDADMAC、Polysciences)、Mw=8,500;ポリ(4−スチレンスルホン酸)、Mw=75,000(PSS、シグマアルドリッチ);ポリ(3,4−エチレンジオキシチオフェン)−ポリ(スチレンスルホネート)、高導電性等級(PEDOT:PSS、シグマアルドリッチ);TIMCALから得たSuperPLi、およびポリビニリデンフルオリド/n−メチル−2−ピロリドン(PVDF/NMP)の混合物をカソード用スラリーの調製のために使用した。シクロペンタノン、ReagentPlus、≧99%(シグマアルドリッチ)の添加によってスラリーの希釈を行った。電気化学セルに使用した電解質は、無水1,3−ジオキソラン(シグマアルドリッチ)と1,2−ジメトキシエタン(シグマアルドリッチ)との1:1混合液中の1MのLiTFSI塩(3Mから購入)から構成された。
電気化学:上記実施例で得た被覆硫黄粒子、20%のSuperP Li、および3%のPVDF結着剤を含有する、必要に応じてNMP/シクロペンタノンで希釈された80μmのスラリーを、12μmのAl箔集電体上に注ぐことによって、作用電極を作製した。カソード総重量はおおよそ3mgに保った。電極を60℃で24時間乾燥させ、その後、コイン型電池を組立てるために、Arで満たされたグローブボックス内に移した。リチウム金属箔(厚み1mm)をアノードとして使用した。Celgard2325セパレータを有する2032ステンレス鋼製コイン型電池を電気化学測定に使用した。カソード中の硫黄合計量についての理論容量を仮定して充放電速度を計算した。BioLogic SASのVMP3モデル、マルチチャンネルのScience Instrumentsのポテンショスタットを電気化学測定に使用した。データは、Science Instrumentsから提供された、対応するVMP3ファームウェアを有するEC−LabソフトウェアV10.02を使用して処理した。
Claims (19)
- リチウム硫黄電池用のカソードであって、
活物質を含み、
前記活物質は、硫黄材料を含み、
前記硫黄材料は、硫黄元素粒子であるコアをシェル内に含むサブミクロンコア−シェル粒子を含み、
前記シェルは、
前記コアの最も近くにある、少なくとも1つの疎水性領域を有するイオン的に帯電した自己組織化導電性コポリマーの第1層と、
前記第1層に隣接およびイオン結合し、前記第1層とは相反する電荷を有する、少なくとも第2の導電性ポリマー層とを含み、
前記コアは、前記コア内に分散している官能基化導電性炭素材料の粒子を含む、カソード。 - 導電性基材である金属箔をさらに含み、
前記活物質は前記金属箔上に塗布されている、請求項1に記載のカソード。 - 前記官能基化導電性炭素材料が、−COOHで官能基化されたケッチェンブラックである、請求項1に記載のカソード。
- カソードの前記活物質の硫黄元素含有量が、カソードの前記活物質総重量の75重量%以上である、請求項1に記載のカソード。
- リチウム金属を含むアノードと;
請求項1に記載のカソードと
を含む、リチウム硫黄電池。 - 前記官能基化導電性炭素材料が、−COOHで官能基化されたケッチェンブラックである、請求項5に記載のリチウム硫黄電池。
- カソードの前記活物質の硫黄元素含有量が、カソードの前記活物質総重量の75重量%以上である、請求項5に記載のリチウム硫黄電池。
- 請求項5に記載のリチウム硫黄電池を備えた車両。
- 前記硫黄材料の硫黄元素含有量が、少なくとも95重量%である、請求項1に記載のカソード。
- 前記コア内に分散している前記官能基化導電性炭素材料の粒子の含有量が、前記コア−シェル粒子の0.1〜5重量%である、請求項1に記載のカソード。
- 外側の導電性ポリマー層の表面上にあるかまたは埋め込まれている前記官能基化導電性炭素材料の粒子をさらに備え、前記官能基化導電性炭素材料の含有量が、前記コア−シェル粒子の0.1〜5重量%である、請求項1に記載のカソード。
- 前記コアは、直径が1マイクロメートル未満である、請求項1に記載のカソード。
- 少なくとも1つの疎水性領域を有する前記自己組織化導電性コポリマーが、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)とポリスチレンスルホネート(PSS)とのポリマー塩である、請求項12に記載のカソード。
- 前記第2の導電性ポリマー層がポリジメチルジアリルアンモニウムクロリド(PDADMAC)を含む、請求項13に記載のカソード。
- PEDOT−PSSおよびPDADMACの合計7つの交互の層を含む、請求項14に記載のカソード。
- 前記官能基化導電性炭素材料の粒子の含有量が、前記コア−シェル粒子の0.1〜5重量%である、請求項5に記載のリチウム硫黄電池。
- 外側の導電性ポリマー層の表面上にあるかまたは埋め込まれている前記官能基化導電性炭素材料の粒子をさらに備え、前記官能基化導電性炭素材料の粒子の含有量が、前記コア−シェル粒子の0.1〜5重量%である、請求項5に記載のリチウム硫黄電池。
- 少なくとも1つの疎水性領域を有する前記自己組織化導電性コポリマーが、ポリ(3,4−エチレンジオキシチオフェン)(PEDOT)とポリスチレンスルホネート(PSS)とのポリマー塩であり、析出された硫黄元素の前記コアは、直径が1マイクロメートル未満である、請求項5に記載のリチウム硫黄電池。
- 前記第2の導電性ポリマー層がポリジメチルジアリルアンモニウムクロリド(PDADMAC)を含む、請求項5に記載のリチウム硫黄電池。
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US20160087266A1 (en) | 2016-03-24 |
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