JP2021535551A - アニオン−酸化還元活性複合カソードを備える、再充電可能な高エネルギー電池の製造方法 - Google Patents
アニオン−酸化還元活性複合カソードを備える、再充電可能な高エネルギー電池の製造方法 Download PDFInfo
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- JP2021535551A JP2021535551A JP2021509182A JP2021509182A JP2021535551A JP 2021535551 A JP2021535551 A JP 2021535551A JP 2021509182 A JP2021509182 A JP 2021509182A JP 2021509182 A JP2021509182 A JP 2021509182A JP 2021535551 A JP2021535551 A JP 2021535551A
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- Prior art keywords
- lithium
- conductive
- transition metal
- metal oxide
- mixed
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 88
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 82
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 37
- 150000003624 transition metals Chemical class 0.000 claims abstract description 32
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 28
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 20
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 15
- -1 LiMnNiO 2 Inorganic materials 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 claims description 13
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 13
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 12
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 239000003623 enhancer Substances 0.000 claims description 9
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 9
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000006182 cathode active material Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000007770 graphite material Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910018871 CoO 2 Inorganic materials 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000010450 olivine Substances 0.000 claims 2
- 229910052609 olivine Inorganic materials 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010586 diagram Methods 0.000 abstract 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000010405 anode material Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910009515 Li1.5Al0.5Ti1.5(PO4)3 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910020091 MgCa Inorganic materials 0.000 description 2
- 229910017958 MgNH Inorganic materials 0.000 description 2
- 101100003996 Mus musculus Atrn gene Proteins 0.000 description 2
- GRQJZSJOACLQOV-UHFFFAOYSA-N [Li].[N] Chemical compound [Li].[N] GRQJZSJOACLQOV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910000045 transition metal hydride Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003000 Li(Ni,Mn,Co)O2 Inorganic materials 0.000 description 1
- 229910010499 Li2.9PO3.3N0.36 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 101100454869 Rattus norvegicus Lhx5 gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000007514 bases Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 108010051489 calin Proteins 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OGGXGZAMXPVRFZ-UHFFFAOYSA-N dimethylarsinic acid Chemical compound C[As](C)(O)=O OGGXGZAMXPVRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000002223 garnet Substances 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
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- PIHTXGRVQBTVRE-KFYAXVMHSA-N olivin Chemical group OC1=CC(O)=C2C(O)=C(C(=O)[C@H]([C@H]([C@H](OC)C(=O)[C@@H](O)[C@@H](C)O)C3)O)C3=CC2=C1 PIHTXGRVQBTVRE-KFYAXVMHSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- WAWVSIXKQGJDBE-UHFFFAOYSA-K trilithium thiophosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=S WAWVSIXKQGJDBE-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
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Abstract
Description
市販の再充電可能なリチウムイオン電池が作動する原理は、挿入機構に基づいている。負極(アノード)と正極(カソード)の両方には、微細構造を根本的に変えることなく、リチウムイオンをインターカレート(挿入)できる材料が使用されている。アノード材料がグラファイトや硬質炭素などの炭素系材料であるのに対し、カソード活性材料は遷移金属酸化物からなる。遷移金属酸化物の遷移金属は、酸化還元活性である。すなわち、充放電中に酸化状態を変化させる。これは、以下の代表的な反応で示される。
Li++e−+O2 −> LiO2
Li2O2 −> 2Li++2e−+O2
る。そのうえ、充電電位と放電電位の間には通常0.5〜1Vの強いギャップが存在するため、エネルギー効率(「往復効率」)はまったく満足のいくものではない。現在の技術的な課題は、リチウム/空気電池の商業化が早くても10〜20年後になり得ることを意味する。概説については、K.Amine et al.,Chem.Reviews2014,5611−40,114を参照のこと。
chem.Soc.1993,93−23)(Proc.Symp.New Sealed Rech.Batt.and Supercapacitors,1993,389−400)。
本発明が解決しようとする課題は、特にモバイルアプリケーション用に十分に高い、少なくとも500Wh/kgのエネルギー密度を確実にすることができる、製造方法及び電気化学的貯蔵システムを提供することである。更に、商業的に容易に入手可能で、安全に管理可能な活性材料であって、希少金属または入手困難な金属の含有量が可能な限り低い
ものを使用することが好ましい。
本発明の課題は、アニオン−酸化還元活性複合カソードを備える再充電可能な高エネルギー電池の製造方法によって解決される。そこで、アニオン−酸化還元活性複合カソードは、電気化学的に活性な成分として水酸化リチウムを含有し、それは、電子導電性または混合導電性の遷移金属及び/または遷移金属酸化物と混合されて接触される。そうすると、電子導電性または混合導電性ネットワークが形成され、この混合物が電流ドレインに適用され、こうして形成された複合カソードが、セパレータ、リチウム導電性電解質及びリチウム含有負極と共に電池ケーシング内に配置され、電気化学電池が得られる。これは、少なくとも1回の初期形成サイクルを受ける。正極(カソード)が、電気化学的に活性な成分として少なくとも水酸化リチウム(LiOH)、ならびに所望により酸化リチウム(Li2O)、過酸化リチウム(Li2O2)及び/またはリチウム超過酸化物(LiO2)から選択される、リチウム化合物を含有する、複合材料からなる、再充電可能な高エネルギー電池の場合、カソードは、少なくとも最初の放電サイクルの後に(すなわち、リチウム過剰状態に)水素化リチウム(LiH)を更に含有する。このLiHは、後述する式(1)〜(3)のいずれかに従って形成される。電気化学的に活性な成分は、電子導電性または混合導電性ネットワーク内に埋め込まれており、それは、遷移金属粒子及び/または電子導電性遷移金属酸化物、ならびに所望により他の導電性増強材料を含む。
応する。
LiOH+2Li++2e− −> Li2O+LiH (1)
2LiOH+2Li++2e− −> Li2O2+2LiH (2)
2LiOH+Li++e− −> LiO2+2LiH (3)
LiH −> 1/2H2+Li++e− (4)
LiO2+Li++e− <=> Li2O2 (5)
Li2O2+2Li++2e− <=> 2Li2O (6)
LiO2+3Li++3e− <=> 2Li2O (7)
素化合物のナノ粒子状形態、及びLi/Li+に対して2Vを超える電気化学的電位を有する電子導電性もしくは混合導電性遷移金属または遷移金属酸化物化合物がこのようにして得られる。ナノ粒子状の粒子形態は更に、代替的な物理的処理(蒸着法、プラズマ法及びレーザー法)、または化学的処理、例えば溶媒系処理、好ましくはゾル/ゲル処理によって製造することができる。
表の第3族から第12族の金属、及びM’=周期表の第3族から第12族の少なくとも1つの更なる遷移金属、及び/またはリチウム元素(LiyMNx)を有する遷移金属窒化物(ニトリドメタレート)(MM’yNx)であって、ここでy=0〜8、x=0.5〜1;一般式
LiM2 z(NH)0.5x+z (I)及び
LimM2 n(NH2)1+n (II)であって、
ここで、
(I)及び(II)は任意の混合比で存在することができ、
M2=アルカリ土類元素(Mg、Ca、Sr、Ba、またはこれらの任意の混合物)であり、
x=0〜4、z=0〜2であり、
m=1または0であり、n=1または0であり、ここで(m+n)=1である、金属窒素化合物;であり得る。
Li2z+xM2 z(NH)0.5x+z (III)
Li3N・n(LiM2N)・(4−2m)LiH (IV)
ここで、
(III)及び(IV)は任意の混合比で存在することができ、
M2=アルカリ土類元素(Mg、Ca、Sr、Ba、またはこれらの任意の混合物)であり、
x=0〜4、z=0〜2であり、
m=1または0であり、n=1または0であり、ここで(m+n)=1である。
リチウム金属(好ましくはコーティングされた、すなわち、表面不動態化された、粉末状または薄い箔として)またはリチウム過剰化合物(例えば、リチウムグラファイト(LiC6−δ、δ=0〜5)またはコーティングされたリチウムケイ化物(LinSiOx@Li2O))をリチウム供与添加剤として使用することができる。結合剤としては、通常電極製造に用いられる有機ポリアミドを使用できる。これらには、PTFE、PVdF、ポリイソブチレン(例えば、BASF製Oppanole(登録商標))、及び類似の材料が含まれる。窒素含有及び遷移金属含有の複合アノード材料にて、一方の微粉化された遷移金属または電子導電性または混合導電性遷移金属化合物LiwMxM’yEz(E=N、C、H;w、y=0〜8;x=0.5〜1;z=0〜3)と他方の窒素含有電気化学的に活性な窒素含有アノード材料との重量比は、一般的に1:100〜1:2の間である。すぐに使用できる(完全な)窒素含有及び遷移金属含有複合アノードは更に、他の導電性向上剤(30wt%まで)、結合剤(20wt%まで)及び/またはプレリチウム化剤(20wt%まで)を含んでもよい。
遷移金属酸化物とカーボンブラック)
Arで満たされたグローブボックスにて、0.9gのCo3O4(50nm未満、供給元Aldrich)、3.6gの無水水酸化リチウム粉末(供給元Albemarle Germany)、及び0.2gのカーボンブラック(AB400)を、ビーカー中で予め混合した。均質化された混合物を、約27gの3mmジルコニアセラミックボールと一緒に50mLのジルコニアセラミック粉砕ビーカーに充填して、密封した。次いで、混合物を遊星ボールミル(Fritsch製Pulverisette P7)で毎分900回転(rpm)で240分間粉砕した。
1.2gの塩化コバルト(Aldrich製97%)、0.69gの過酸化リチウム(Albemarle Germany製93%未満)及び3.6gの無水水酸化リチウム粉末(Albemarle Germany)を、50mlの無水エタノールに溶解または懸濁させて、高エネルギー撹拌器(Ultraturrax IKA T65)を用いて15分間均質化した。得られた懸濁液をRTで4時間磁気撹拌し、次いで濾過した。
Claims (15)
- アニオン−酸化還元活性複合カソードを備える再充電可能な高エネルギー電池の製造方法であって、
電気化学的に活性な成分として水酸化リチウムを含み、
前記水酸化リチウムは、電子導電性または混合導電性遷移金属及び/または遷移金属酸化物と混合されて接触して存在し、電気導電性または混合導電性ネットワークが形成され、
前記混合物を電流ドレインに適用し、形成された前記複合カソードを、セパレータ、リチウム導電性電解質、及びリチウム含有アノードと共に電池筐体内に配置して、電気化学電池が存在し、前記電気化学電池が少なくとも1つの初期形成サイクルを受ける、
ことを特徴とする、前記方法。 - 前記水酸化リチウムが、酸化リチウム、過酸化リチウム及びリチウム超酸化物から選択されるリチウム酸素化合物と更に混合され、
電気化学的に未改質の前記複合カソード材料中のLiOHの割合が、リチウム酸素化合物の総含有量に基づいて少なくとも10mol%、好ましくは少なくとも30mol%であることを特徴とする、請求項1に記載の方法。 - 一方の微粉化された前記電子導電性または混合導電性ネットワーク成分と、他方のLiOH、Li2O、Li2O2及びLiO2から選択されるリチウム酸素化合物に基づく前記カソード活性材料とを、1:100〜1:1、好ましくは1:50〜1:1.5のモル比で使用し、
前記ネットワークを形成する材料の電子導電性が室温で少なくとも10−7秒/cm、好ましくは少なくとも10−6秒/cm、特に好ましくは少なくとも10−5秒/cmであることを特徴とする、請求項1または2に記載の方法。 - 前記遷移金属粒子が、好ましくは元素周期表の第3族から第12族の元素、特に好ましくはM=Sc、Ti、Zr、Hf、V、Cr、Mo、W、Mn、Fe、Co、Ni、Cu、Ag、Zn、及び希土類金属La、Ce、Pr、Nd、Sm、Gd、Dy、Ho、Er、Tm、Yb、Lu、または前記遷移金属の任意の所望の混合物から選択されることを特徴とする、請求項1〜3に記載の方法。
- 前記導電性遷移金属酸化物が、二元金属酸化物、層状構造リチウム金属酸化物、スピネル構造リチウム金属酸化物、逆スピネル構造リチウム金属酸化物、及び/またはオリビン構造リチウム金属酸化物から選択されることを特徴とする、請求項1〜4に記載の方法。
- 前記二元金属酸化物が、チタン酸化物(TiO、Ti2O3)、バナジウム酸化物(V2O3、VO、VO2)、鉄酸化物(Fe3O4、FeO)、コバルト酸化物(CoO2、Co3O4)、Ni2O3、マンガン酸化物(MnO2、Mn3O4)、クロム酸化物(CrO2、Cr3O3)、NbO;LiCoO2、LiNiO2、Li(Ni,Mn,Co)O2、LiV3O8からの前記層状構造リチウム金属酸化物;LiMn2O4、LiMnNiO2、LiNi0.5Mn1.5O4、LiV3O5からの前記スピネル構造リチウム金属酸化物;LiNiVO4、LiCoVO4からの前記逆スピネル構造リチウム金属酸化物;LiFePO4、LiVPO4からの前記オリビン構造リチウム金属酸化物から選択されることを特徴とする、請求項5に記載の方法。
- 前記遷移金属粒子及び/または前記導電性遷移金属酸化物化合物、ならびに前記電気化学的に活性なリチウム酸素化合物が、0.1〜100nm、好ましくは1〜30nmの範囲の粒径を有する微粉化された非晶質またはナノ粒子状の形態で均一に混合されて存在す
ることを特徴とする、請求項1〜6に記載の方法。 - 金属リチウムが前記アノードとして使用されており、
前記リチウムが、シート状金属もしくは粉末電極として、またはシリコン、スズ、ホウ素及びアルミニウムから選択される金属との合金として存在することを特徴とする、請求項1〜7に記載の方法。 - 最初の放電サイクルの前に、前記アノードから電気化学的に抽出可能な、電気化学的に活性化可能なリチウムのモル量が前記アノード内に導入され、
前記モル量が、前記複合カソードに存在する前記LiOH含有量のモル量の少なくとも半分、好ましくは少なくとも同じ、特に好ましくは少なくとも2倍に相当することを特徴とする、請求項1〜8に記載の方法。 - 非金属系導電性増強剤及び結合剤が、前記アニオン−酸化還元活性複合体カソードに使用され、所望により前記アノードにも使用されることを特徴とする、請求項1〜9に記載の方法。
- 前記非金属系導電性増強剤として、グラファイト、硬質炭素、カーボンブラック及びグラフェンなどのグラファイト材料が使用されることを特徴とする、請求項10に記載の方法。
- 前記アニオン−酸化還元活性複合カソード及び前記アノードの両方が、プレス処理またはカレンダー処理によって圧縮されることを特徴とする、請求項1〜11に記載の方法。
- 前記アニオン−酸化還元活性複合カソードの固体成分が、好ましくは高エネルギーミルを用いた粉砕工程によって粉砕され、互いに密接に接触させられることを特徴とする、請求項1〜12に記載の方法。
- アニオン−酸化還元活性複合カソードを備える高エネルギー電池であって、
前記カソードが、最初の電気化学的放電の前に、電気化学的に活性な成分として、電子導電性遷移金属及び/または遷移金属酸化物からなる電子導電性または混合導電性ネットワークに埋め込まれた、少なくとも水酸化リチウム、ならびに所望により酸化リチウム、過酸化リチウム及び/またはリチウム超過酸化物から選択されるリチウム酸素化合物を更に含む、複合材料からなり、
一方の前記電子導電性または混合導電性ネットワーク成分と、他方のLiOH、Li2O、Li2O2及びLiO2から選択されるリチウム酸素化合物に基づく前記カソード活性材料とが、1:100〜1:1、好ましくは1:50〜1:1.5のモル比で存在することを特徴とする、前記高エネルギー電池。 - 前記アノードが、金属リチウム、リチウム含有金属合金、リチウムニトリド遷移金属酸塩、または前記電気化学的に活性な成分が金属窒素化合物である複合材料から選択される、Li/Li+基準電極に対して2V未満の電気化学的電位を有する少なくとも1つのリチウム供与成分または化合物を含み、後者が遷移金属を含有する電子導電性または混合導電性ネットワークに埋め込まれていることを特徴とする、請求項14に記載の高エネルギー電池。
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