WO2022025212A1 - 全固体リチウムイオン二次電池用正極活物質とその製造方法 - Google Patents
全固体リチウムイオン二次電池用正極活物質とその製造方法 Download PDFInfo
- Publication number
- WO2022025212A1 WO2022025212A1 PCT/JP2021/028186 JP2021028186W WO2022025212A1 WO 2022025212 A1 WO2022025212 A1 WO 2022025212A1 JP 2021028186 W JP2021028186 W JP 2021028186W WO 2022025212 A1 WO2022025212 A1 WO 2022025212A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel composite
- composite oxide
- lithium
- particles
- positive electrode
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 91
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 239000002131 composite material Substances 0.000 claims abstract description 225
- 239000002245 particle Substances 0.000 claims abstract description 184
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims abstract description 167
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000011247 coating layer Substances 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 56
- 239000010955 niobium Substances 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 29
- 239000011164 primary particle Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 19
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 16
- 150000002822 niobium compounds Chemical class 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000011163 secondary particle Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 nickel compound compound Chemical class 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000002642 lithium compounds Chemical class 0.000 claims description 7
- 238000004448 titration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 description 55
- 239000007864 aqueous solution Substances 0.000 description 47
- 239000007784 solid electrolyte Substances 0.000 description 44
- 239000012298 atmosphere Substances 0.000 description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 37
- 239000001301 oxygen Substances 0.000 description 37
- 239000000470 constituent Substances 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 23
- 239000002994 raw material Substances 0.000 description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003570 air Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 229910008029 Li-In Inorganic materials 0.000 description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 2
- 229910006670 Li—In Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 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 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000252073 Anguilliformes Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910008745 Li2O-B2O3-P2O5 Inorganic materials 0.000 description 1
- 229910008523 Li2O-B2O3-ZnO Inorganic materials 0.000 description 1
- 229910008590 Li2O—B2O3—P2O5 Inorganic materials 0.000 description 1
- 229910008627 Li2O—B2O3—ZnO Inorganic materials 0.000 description 1
- 229910012316 Li3.6Si0.6P0.4O4 Inorganic materials 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012804 Li3PO4—Li2S—Si2S Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012050 Li4SiO4-Li3PO4 Inorganic materials 0.000 description 1
- 229910012053 Li4SiO4-Li3VO4 Inorganic materials 0.000 description 1
- 229910012069 Li4SiO4—Li3PO4 Inorganic materials 0.000 description 1
- 229910012072 Li4SiO4—Li3VO4 Inorganic materials 0.000 description 1
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 description 1
- 229910013184 LiBO Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910010855 LiI—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910010847 LiI—Li3PO4-P2S5 Inorganic materials 0.000 description 1
- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012254 LiPO4—Li2S—SiS Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 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
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical compound [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M4/131—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
- H01M4/13—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
-
- 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
- H01M4/48—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode active material for an all-solid-state lithium ion secondary battery and a method for producing the same.
- the positive electrode active material is a lithium transition metal composite oxide such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4
- the negative electrode active material is a lithium metal, a lithium alloy, or a metal oxide. Carbon or the like is used.
- a non-aqueous electrolyte solution for example, an electrolytic solution obtained by dissolving Li salts such as LiClO 4 and LiPF 6 in an organic solvent such as ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate as supporting salts is used.
- Li salts such as LiClO 4 and LiPF 6
- organic solvent such as ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate
- non-aqueous electrolytes in particular are factors that limit battery performance such as high-speed charging, thermal stability, and life due to chemical properties such as heat resistance and potential windows. .. Therefore, we are currently researching and developing an all-solid-state lithium-ion secondary battery (hereinafter, also referred to as "all-solid-state battery") that has improved the above-mentioned battery performance by using a solid electrolyte instead of a non-aqueous electrolyte solution as the electrolyte. Is being actively carried out.
- Patent Document 1 describes that among solid electrolytes, sulfide solid electrolytes have high conductivity of lithium ions during charging and discharging, and are preferable for use in all-solid-state batteries.
- Non-Patent Document 1 for example, when the sulfide solid electrolyte and the positive electrode active material which are oxides come into contact with each other, a reaction occurs at the interface between the solid electrolyte and the positive electrode active material during charging and discharging, and the interface occurs. A high resistance phase is generated and hinders the operation of the all-solid-state battery. This is because the space charge layer is formed at the contact interface due to the change in the conduction ion concentration due to the difference in the electrochemical potential, and the ion conductivity is different from that of the bulk and the resistance is high.
- Patent Document 2 in order to prevent contact between the solid electrolyte and the positive electrode active material (oxide) and suppress the formation of a high resistance phase, a coating layer made of LiNbO 3 is provided on the surface of the positive electrode active material.
- Technology has been proposed.
- Japanese Unexamined Patent Publication No. 2014-056661 Japanese Unexamined Patent Publication No. 2010-170715 Japanese Unexamined Patent Publication No. 2011-116580
- LiNbO3-coated LiCoO2 as cathode material for all solid-state lithium secondary batteries
- LiNiO 2 , LiNi 0.80 Co 0.15 Al 0.05 O 2 , and LiNi 0.6 Co 0.2 Mn 0.2 which have a large charge / discharge capacity, are used. It is preferable to use a positive electrode active material having a high Ni ratio such as O2 . Therefore, the inventors examined the applicability of a positive electrode active material having a high Ni ratio to an all-solid-state lithium-ion secondary battery.
- the present inventors can design a battery in which cells are connected in series when a solid electrolyte is used, so that the energy density of the entire battery is higher than that when a non-aqueous electrolyte solution is used. It has been found that the energy density obtained from the positive electrode active material having a high Ni ratio does not reach the expected energy density or battery capacity, even though the energy density is improved.
- an object of the present invention is to provide a positive electrode active material having a higher battery capacity when a positive electrode active material having a high Ni ratio is used as the positive electrode active material of an all-solid-state battery.
- the positive electrode active material for an all-solid-state lithium ion secondary battery comprising particles of the lithium nickel composite oxide and a coating layer covering the surface of the particles, is the lithium nickel composite oxide.
- ⁇ Y x: y (0.98 ⁇ a ⁇ 1.15, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.03, 0 ⁇ x + y ⁇ 0.5, element M is Co, Al, Mn , Zr, Si, Zn and Ti), and the crystallite diameter calculated by the Scheller method from the diffraction peak assigned to the (003) plane measured by XRD is 140 nm or less.
- the amount of eluted lithium ions obtained by neutralization titration is 0.30% by mass or more and 1.00% by mass or less with respect to the total amount of lithium nickel composite oxide particles, and the coating layer is Li.
- An all-solid-state lithium-ion secondary battery which is a composite oxide containing at least one element selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta and W. Positive positive element for use is provided.
- the particles of the lithium nickel composite oxide include secondary particles formed by aggregating a plurality of primary particles, and have a porous structure having a plurality of void portions in which the primary particles do not exist in the secondary particles.
- the specific surface area measured by the nitrogen adsorption BET method is preferably 0.3 m 2 / g or more and 2.0 m 2 / g or less.
- the particles of the lithium nickel composite oxide preferably have a particle size (D50) of 7 ⁇ m or less, which corresponds to an integrated volume fraction of 50% in the integrated volume distribution curve of the particle size distribution.
- the average thickness of the coating layer is preferably 1 nm or more and 15 nm or less.
- a coating liquid containing at least one element selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta and W is adhered to the surface of the particles of the lithium nickel composite oxide.
- a method for producing a positive electrode active material for an all-solid-state lithium ion secondary battery comprising a coating step of forming a coating layer.
- the nickel composite compound contains a nickel composite oxide, and it is preferable to include an oxidation roasting step of oxidizing and roasting the nickel composite hydroxide prepared by the crystallization reaction to obtain the nickel composite oxide. Further, after the coating step, it is preferable to include a heat treatment step of heat-treating the lithium nickel composite oxide particles having the coating layer formed on the surface at 300 ° C. or higher.
- the positive electrode active material of the present invention When the positive electrode active material of the present invention is used as the positive electrode active material of an all-solid-state battery, the battery capacity is improved. In addition, the production method of the present invention can produce this positive electrode active material with high productivity.
- FIG. 1 is a schematic diagram showing an example of a positive electrode active material according to the present embodiment.
- FIG. 2 is a diagram showing an example of a method for producing a positive electrode active material according to the present embodiment.
- FIG. 3 is a diagram showing an example of a method for producing a nickel composite compound according to the present embodiment. It is explanatory drawing of the cross-sectional structure of the evaluation battery used for the battery evaluation.
- Positive Electrode Active Material for All-Solid Lithium Ion Secondary Battery First, a configuration example of the positive electrode active material for all-solid-state lithium-ion secondary battery (hereinafter, also referred to as “positive electrode active material”) according to the present embodiment will be described.
- FIG. 1 is a diagram schematically showing an example of a positive electrode active material according to the present embodiment.
- the positive electrode active material 10 has particles 1 of a lithium nickel composite oxide and a coating layer 2 covering the surface of the particles 1.
- each component will be described.
- the particles 1 of the lithium-nickel composite oxide have a crystal structure belonging to the space group R-3m, and contain at least lithium (Li), nickel (Ni), elements M, and Nb. It is a composite oxide containing.
- a indicating the Li content ratio is 0.98 ⁇ a ⁇ 1.15
- a is less than 0.98 Li is deficient in the positive electrode active material, which tends to cause a decrease in capacity as a battery material.
- a exceeds 1.15 the crystal structure of the particles 1 of the lithium nickel composite oxide grows excessively, the primary particles become coarse, and the particles 1 are likely to be cracked, so that the durability is likely to be impaired.
- (1-xy) indicating the Ni content ratio is 0.5 or more and less than 1.0.
- the range including the lower limit of the Ni content ratio is preferably 0.6 or more, 0.7 or more, or 0.8 or more.
- (1-xy) is less than 0.5, the battery capacity is low.
- the element M is preferably at least one selected from the group consisting of Co, Al, Mn, Zr, Si, Zn and Ti. Further, the element M preferably contains at least one element selected from cobalt (Co), aluminum (Al), and manganese (Mn). The element M can be appropriately selected depending on the use and required performance of the secondary battery configured by using the positive electrode active material 10.
- x indicating the content ratio of the element M is 0 ⁇ x ⁇ 0.5, preferably 0 ⁇ x ⁇ 0.3, and may be 0 ⁇ x ⁇ 0.2.
- the element M may contain Co and Al.
- the range of Co may be, for example, 0 ⁇ x ⁇ 0.3 or 0 ⁇ x ⁇ 0.2.
- the range of Al may be, for example, 0 ⁇ x ⁇ 0.1 or 0 ⁇ x ⁇ 0.07.
- y indicating the content ratio of Nb is 0 ⁇ y ⁇ 0.03, preferably 0 ⁇ y ⁇ 0.02.
- the all-solid-state battery can have a high battery capacity. If y exceeds 0.03, it may generate less active LiNb 3 O 8 and cause a decrease in battery capacity. Further, for example, when y is 0.001 ⁇ y ⁇ 0.01, it is possible to have a higher battery capacity.
- the niobium contained in the particles 1 of the lithium nickel composite oxide may be solid-solved inside the primary particles or may be present at the interface of the primary particles. It is preferable that at least a part of niobium segregates at the interface of the primary particles. The details of this reason are unknown, but for example, it is said that niobium segregates at the interface of the primary particles, thereby reducing the barrier of movement of Li ions in the secondary particles and improving the battery capacity. is assumed. Further, it is considered that the amount of eluted lithium, which will be described later, can be easily adjusted to a specific range by segregating at least a part of niobium to the interface of the primary particles.
- the lithium nickel composite oxide particle 1 has a crystal structure belonging to the space group R-3m.
- the particles 1 of the lithium nickel composite oxide have a crystal structure belonging to the space group R-3m, an increase in internal resistance can be suppressed in the secondary battery.
- the crystal structure of the particles 1 of the lithium nickel composite oxide can be confirmed by powder X-ray diffraction (XRD) measurement. That is, from the diffraction pattern obtained when the powder X-ray diffraction (XRD) measurement of the particles 1 of the lithium nickel composite oxide is performed, it belongs to the layered rock salt type crystal structure (space group R-3m) of the "R-3m” structure. It is preferable that the peak attributed to the crystal structure) is detected. In particular, it is more preferable that only the peaks attributed to the layered rock salt type crystal structure of the "R-3m" structure are detected from the diffraction pattern.
- XRD powder X-ray diffraction
- the particles 1 of the lithium nickel composite oxide may be a lithium nickel composite oxide single phase having a crystal structure of "R-3m” structure, but may not be a single phase.
- other compounds eg, impurities, etc.
- the intensity of heterogeneous peaks other than the layered rock salt type structure of "R-3m” structure becomes the layered rock salt type structure of "R-3m” structure. It is preferable not to exceed the attributed peak intensity.
- the lithium nickel composite oxide particles 1 preferably have a crystallite diameter of 140 nm or less, and more preferably 40 nm or more and 140 nm or less. Further, the range including the upper limit of the crystallite diameter may be 130 nm or less. Further, the range including the lower limit of the crystallite diameter may be 50 nm or more.
- the crystallite diameter can be calculated by the Scheller method using the peak attributed to (003) of the above XRD diffraction pattern. When the crystallite diameter of the particles 1 of the lithium nickel composite oxide exceeds 140 nm, the diffusion distance in the solid in the crystal may become long and the battery capacity may decrease. Further, when the crystallite diameter of the particles 1 of the lithium nickel composite oxide is less than 40 nm, the crystal structure becomes unstable and the battery capacity tends to decrease.
- the amount of eluted lithium ions obtained by neutralization titration is 0.30% by mass or more and 1.00% by mass or less, and 0.30% by mass or more, based on the total amount of the particles 1. It is preferably 0.70% by mass or less.
- the amount of eluted lithium ions can be determined by a neutralization titration method using hydrochloric acid, which is the amount of lithium ions eluted in water when the particles 1 of the lithium nickel composite oxide are dispersed in water.
- a neutralization titration method a Warder method or a Winkler method can be used as the neutralization titration method.
- the battery capacity may decrease.
- the surface of the lithium nickel composite oxide particles 1 contains a specific amount of eluted lithium ions, so that the lithium nickel composite oxide particles 1 and the solid state are contained in the all-solid-state battery.
- One of the reasons is considered to be that it suppresses direct contact with the electrolyte and suppresses the formation of a high resistance phase.
- the amount of eluted lithium ions increases as compared with the lithium nickel composite oxide containing no niobium. Therefore, for example, by adjusting the niobium content to the above range and the elution lithium amount to 0.3% by mass or more by using the production method described later, a positive electrode active material having a high discharge capacity can be obtained. Obtainable. However, when the amount of eluted lithium ions in the particles 1 of the lithium nickel composite oxide exceeds 1.00% by mass, the discharge capacity decreases.
- the lithium nickel composite oxide particles 1 preferably have a crystallite diameter of 140 nm or less and an eluted lithium ion amount of 0.30% by mass or more.
- the battery capacity may decrease if the amount of eluted lithium ions is less than 0.30% by mass.
- the details of the reason for this are unknown, but it is presumed as follows, for example.
- the lithium nickel composite oxide particle 1 includes secondary particles formed by aggregating a plurality of primary particles.
- the crystallite diameter of the particles 1 of the lithium nickel composite oxide has a positive correlation with the size of the primary particles constituting the secondary particles, and it is considered that the smaller the crystallite diameter, the more particle interfaces between the primary particles. .. Further, the eluted lithium ion is mainly present at the particle interface between the primary particles and the primary particles. Therefore, when the crystallite diameter is small and there are many interfaces of the primary particles, if the number of eluted lithium ions present at the interface (surface) of the primary particles decreases too much, voids are formed at the interface of the primary particles.
- the positive electrode active material When a large number of voids are present at the interface of the primary particles, the positive electrode active material is easily cracked in the process of manufacturing the electrode of the all-solid-state battery, and the contact interface between the lithium nickel composite oxide particles and the solid electrolyte increases. It is considered that the generated phase interferes with the transfer of charges between the electrolyte and the positive electrode active material due to the side reaction that occurs at this increased contact interface, so that the resistance of the battery increases and the battery capacity decreases.
- the crystallite diameter of the lithium nickel composite oxide particle 1 exceeds 140 nm, even if the amount of eluted lithium ions is 0.30% by mass or more, the battery capacity is lowered, which is not preferable. This is because the coarsening of the primary particles reduces the grain boundaries between the primary particles, so that the eluted lithium ions are scattered in a mass on the surface of the secondary particles, and the existence of the eluted lithium ions itself. Is considered to be the resistance phase.
- the crystallite diameter and the amount of eluted lithium can be adjusted within the above ranges by using, for example, a method for producing a positive electrode active material described later.
- the lithium nickel composite oxide particle 1 includes secondary particles formed by aggregating a plurality of primary particles. Further, the lithium nickel composite oxide particle 1 may contain a single primary particle or may be a mixture of a single primary particle and a secondary particle.
- the average particle size of the secondary particles is preferably 3.0 ⁇ m or more and 7.0 ⁇ m or less. Further, it is preferable that the secondary particles are formed by aggregating a large number of primary particles having a particle size of 0.1 ⁇ m or more and 2.0 ⁇ m or less. When a single primary particle is contained, the primary particle preferably has a particle size of 1.0 ⁇ m or more and 7.0 ⁇ m or less.
- the average particle size of each particle can be obtained by, for example, calculating the average of the diameters corresponding to the area circles of 20 or more particles.
- the particles 1 of the lithium nickel composite oxide have a particle size (D50, hereinafter also referred to as “average particle size D50”) corresponding to an integrated volume fraction of 50% in the integrated volume distribution curve of the particle size distribution of 7 ⁇ m or less. It is preferably 2 ⁇ m or more and 7 ⁇ m or less, and more preferably 3 ⁇ m or more and 7 ⁇ m or less.
- the average particle size (D50) can be measured with a laser light diffraction / scattering type particle size distribution meter.
- the secondary battery using the positive electrode active material 10 as the positive electrode can sufficiently increase the battery capacity per battery capacity, and Excellent battery characteristics such as thermal stability and high output can be obtained.
- the average particle size D50 is 2 ⁇ m or less, it is not preferable because it tends to aggregate when the coating layer 2 is applied.
- [(D90-d10) / volume average particle size Mv] which is an index showing the spread of the particle size distribution of the particles 1 of the lithium nickel composite oxide, is not particularly limited, but is 0. It may be 7 or less, 0.6 or less, or 0.55 or less.
- the lower limit of [(d90-d10) / volume average particle size Mv] is not particularly limited, but is, for example, 0.3 or more.
- [(d90-d10) / volume average particle size Mv] may be 0.7 or more from the viewpoint of filling property, and is relatively uniform by using the method for producing a positive electrode active material described later.
- the coating layer 2 can be coated.
- d10 means a particle size in which the number of particles at each particle size is accumulated from the smaller particle size side, and the cumulative volume is 10% of the total volume of all particles, and d90 means the number of particles is similarly accumulated. However, it means a particle size in which the cumulative volume is 90% of the total volume of all particles. Further, d10, d90 and the volume average particle size Mv can be obtained from the volume integrated value measured by the laser light diffraction / scattering type particle size analyzer as in the case of the average particle size D50.
- the specific surface area of the particles 1 of the lithium nickel composite oxide is not particularly limited, and may be, for example, 0.3 m 2 / g or more and 2.0 m 2 / g or less, and 0.3 m 2 / g or more and 1.0 m. It may be 2 / g or less. When the specific surface area is in the above range, the output characteristics are good.
- the specific surface area can be measured by the nitrogen adsorption BET method.
- the positive electrode active material 10 includes a coating layer 2 on the surface of the particles 1 of the lithium nickel composite oxide. By having the coating layer 2 on the surface of the particles 1, the interaction between the positive electrode active material 10 and the solid electrolyte can be suppressed in the secondary battery provided with the positive electrode containing the positive electrode active material 10.
- the coating layer 2 is a composite containing lithium (Li) and one or more elements selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta, and W. It is an oxide.
- the constituent elements of the coating layer 2 other than lithium (Li) and oxygen (O) may be one kind or two or more kinds.
- the coating layer 2 may be, for example, a composite oxide composed of Li and Ti, or may be a composite oxide composed of Li and Nb.
- the coating amount of the coating layer 2 is not particularly limited, but the coating amount can be adjusted according to the specific surface area (m 2 / g) of the particles 1 of the lithium nickel composite oxide to be coated.
- the coating layer 2 has, for example, the constituent elements (excluding Li and O) of the coating layer 2 at a ratio of preferably 30 ⁇ mol or more and 600 ⁇ mol or less, more preferably 50 ⁇ mol or more and 400 ⁇ mol or less, per 1 m 2 of the surface area of the lithium nickel composite oxide particles 1. ) Is more preferable.
- the entire surface of the lithium nickel composite oxide particles 1 is coated.
- the layer 2 can be uniformly arranged.
- the coating layer 2 the reaction between the particles 1 of the lithium nickel composite oxide and the solid electrolyte can be suppressed, but at the same time, the internal resistance of the secondary battery may increase.
- the content of the constituent elements (excluding Li and O) of the coating layer 2 per 1 m 2 of the surface area of the lithium nickel composite oxide particles 1 is 600 ⁇ mol or less, the coating layer 2 becomes the lithium nickel composite oxide particles 1. It is possible to suppress the obstacle of the lithium intercalation / deintercalation reaction and reduce the internal resistance.
- the method for evaluating and calculating the content of the constituent elements (excluding Li and O) of the coating layer 2 in the coating layer 2 is not particularly limited, but can be obtained, for example, as follows.
- the content of the constituent elements (excluding Li and O) of the coating layer 2 in 1 g of the positive electrode active material is measured by a method such as chemical analysis.
- a method of chemical analysis measurement is performed by ICP (Inductively Coupled Plasma) emission spectroscopy or the like.
- the specific surface area of the particles 1 of the lithium nickel composite oxide before coating the coating layer 2 is measured by a nitrogen adsorption BET method or the like.
- lithium is divided by the specific surface area (m 2 / g) of the particles 1 of the lithium nickel composite oxide by dividing the content of the constituent elements (excluding Li and O) of the coating layer 2 in 1 g of the positive electrode active material.
- the content of the constituent elements (excluding Li and O) of the coating layer 2 per 1 m 2 of the surface area of the nickel composite oxide particles 1 can be determined.
- the lithium nickel composite oxide particles 1 contain the constituent elements (excluding Li and O) of the coating layer 2, the difference in the contents of the constituent elements (excluding Li and O) of the coating layer 2 before and after the coating. Can be used as the content of the constituent elements (excluding Li and O) of the coating layer 2 used for the coating.
- the average thickness of the coating layer is, for example, preferably 2 nm or more and 20 nm or less, more preferably 2 nm or more and 15 nm or less, and further preferably 5 nm or more and 15 nm or less.
- the average thickness of the coating layer 2 can be observed with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like, or an energy dispersion type X-ray spectroscope (EDS) or electron energy loss spectroscopy attached thereto. It can be calculated by analyzing with a spectroscope such as the method (EELS) and measuring a layer uniformly formed on the surface of the particles 1 of the lithium nickel composite oxide.
- a spectroscope such as the method (EELS)
- the coating layer 2 preferably exists adjacent to the surface of the particles 1 of the lithium nickel composite oxide. Whether or not the coating layer 2 is present adjacent to the surface of the particles 1 depends on whether or not the compound containing the constituent elements of the coating layer 2 is released from the surface of the particles 1 of the lithium nickel composite oxide. I can judge. When the coating layer 2 is released from the surface of the particles 1 of the lithium nickel composite oxide, it does not electrochemically contribute to the battery capacity, which is a factor of lowering the battery capacity per weight.
- the coating layer 2 and the surface of the lithium nickel composite oxide particles 1 do not have to have a clear boundary line.
- the coating layer 2 is the constituent elements of the coating layer 2 (excluding Li and O). ) Is detected, and may include a region in which both the constituent elements (excluding Li and O) of the coating layer 2 and the constituent elements of the lithium nickel composite oxide particle 1 are detected.
- the region on the surface side of the particles constituting the positive electrode active material 10 is lithium. It refers to a region (site) in which the concentration of constituent elements (excluding Li and O) of the coating layer 2 is higher than that of the central portion of the particles 1 of the nickel composite oxide.
- the constituent elements (excluding Li and O) of the coating layer 2 may be partially dissolved from the surface of the particles of the lithium nickel composite oxide to the inside.
- a heat treatment step (S40) is performed after the coating step (S30), and depending on the conditions at that time, the coating layer constituent elements of the coating layer can be diffused into the lithium nickel composite oxide.
- the coating layer 2 when the coating layer 2 contains Ti and / or Nb, the coating layer 2 is simply a solid electrolyte due to the solid dissolution of Ti and / or Nb from the surface of the particles 1 of the lithium nickel composite oxide to the inside.
- the effect of preventing direct contact between the lithium nickel composite oxide particles 1 and the lithium nickel composite oxide particles 1 not only reduces the chance of reaction, but also reduces the reactivity between the surface layer of the lithium nickel composite oxide particles 1 and the solid electrolyte. Produces.
- the method for producing a positive electrode active material according to the present embodiment includes a mixing step (S10) of mixing a nickel compound compound, a niobium compound, and a lithium compound to obtain a mixture, and firing the mixture.
- a firing step (S20) for obtaining particles of the lithium nickel composite oxide and a coating step (S30) for adhering a coating liquid to the surface of the particles of the lithium nickel composite oxide to form a coating layer are provided.
- a heat treatment step (S40) may be provided in which the particles of the lithium nickel composite oxide having the coating layer formed on the surface are heat-treated at 300 ° C. or higher.
- the nickel composite compound may be a nickel composite oxide obtained by oxidatively roasting a nickel composite hydroxide prepared by a crystallization reaction.
- the nickel composite compound can be produced by a method including a crystallization step (S1) and an oxidative roasting step (S2).
- S1 crystallization step
- S2 oxidative roasting step
- each step will be described in detail.
- the following description is an example of a manufacturing method, and does not limit the manufacturing method.
- Crystallization step (S1) In the crystallization step (S1), a nickel composite hydroxide which is a precursor of the lithium nickel composite oxide is prepared by a crystallization reaction.
- the substance amount ratio of each element is equal to the substance amount ratio of each element contained in the particles of the target lithium nickel composite oxide.
- a raw material aqueous solution is prepared, and the prepared raw material aqueous solution, an alkali metal aqueous solution and an ammonium ion feeder are both supplied to a reaction vessel and subjected to a neutralization crystallization reaction to obtain a nickel composite hydroxide.
- the raw material of each element may be, for example, simultaneously dissolved in water to produce a raw material aqueous solution as a mixed aqueous solution. Further, an individual aqueous solution may be prepared for each raw material of each element to prepare an individual aqueous solution of the raw material. If it is inconvenient to prepare the raw material aqueous solution as a mixed aqueous solution, it is preferable to prepare an individual raw material aqueous solution for each raw material. For example, when the liquidity of the aqueous solution of each raw material is divided into acidic and basic, it is preferable to prepare an individual raw material aqueous solution for each raw material.
- the metal compound used as a raw material for each element may be water-soluble, and sulfates, chlorides, nitrates, etc. can be used, but inexpensive sulfates are preferable from the viewpoint of cost. If a suitable water-soluble metal compound is not found in the element M or the like, it may be added in the oxidative roasting step (S2) or the mixing step (S10) described later without adding it to the mixed aqueous solution of the raw materials. good.
- the alkali metal aqueous solution is not particularly limited, but one or more selected from the group consisting of sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, and potassium carbonate can be preferably used.
- the ammonium ion feeder is not particularly limited, but one or more selected from aqueous ammonia, aqueous solution of ammonium carbonate, aqueous solution of ammonium chloride, and aqueous solution of ammonium sulfate can be preferably used.
- the shape of the reaction vessel is not particularly limited, but a cylindrical container having a baffle plate inside, and a stirrer and a temperature controller are preferable.
- the stirrer is preferably equipped with a motor, a shaft and a stirrer blade.
- the temperature controller is preferably of a type in which a heat medium is circulated outside the cylindrical container to heat or cool the cylindrical container.
- the pH and the ammonia concentration are maintained at constant values.
- the pH of the aqueous solution in the reaction vessel is preferably adjusted to be 11.0 or more and 12.2 or less based on the liquid temperature of 25 ° C.
- impurities due to anions constituting the metal compound contained in the raw material aqueous solution used may be mixed in the nickel composite hydroxide.
- the pH value of the initial aqueous solution (inside the reaction vessel) is 11.0 or higher, it is possible to suppress the contamination of impurities caused by anions.
- the pH of the initial aqueous solution to 12.2 or less, it is possible to suppress the formation of fine particles of the obtained nickel composite hydroxide and obtain a composite hydroxide having a particle size suitable for the charge / discharge reaction. ..
- the ammonia concentration of the aqueous solution in the reaction vessel is preferably adjusted to 5 g / L or more and 20 g / L or less.
- the ammonia concentration is 5 g / L or more, Ni in the raw material aqueous solution (mixed aqueous solution) becomes an ammonium complex, and the precipitation rate decreases from the liquid phase to the solid phase as a hydroxide, so that the obtained nickel composite hydroxide is obtained. Increases the sphericality of the particles.
- the ammonia concentration is 20 g / L or less, the solubility of nickel forming an ammonium complex is suppressed from being excessively increased, and the substance amount ratio of the obtained nickel composite hydroxide is more reliably targeted. Can be a ratio. In addition, it is industrially preferable because it can suppress excessive consumption of ammonia.
- the atmosphere in the reaction vessel is preferably a non-oxidizing atmosphere, for example, an atmosphere having an oxygen concentration of 1% by volume or less.
- a non-oxidizing atmosphere it is possible to suppress the oxidation of the raw material compound and the like. For example, it is possible to prevent oxidized cobalt and manganese from precipitating as fine particles.
- the temperature in the reaction vessel in the crystallization step (S1) is preferably maintained at 40 ° C. or higher and 60 ° C. or lower, more preferably 45 ° C. or higher, still more preferably 55 ° C. or lower.
- the temperature of the reaction tank rises due to the heat of reaction and the Joule heat of stirring, by setting the temperature inside the reaction tank to 40 ° C or higher, no extra energy is consumed for cooling. Further, by setting the temperature in the reaction vessel to 60 ° C. or lower, the evaporation of ammonia from the initial aqueous solution and the reaction aqueous solution can be suppressed, and it becomes easy to maintain the target ammonia concentration.
- Lithium-nickel composite oxide particles preferably have a narrow particle size distribution and a uniform particle size. In order to produce such particles, it is necessary to obtain particles having a uniform particle size in the nickel composite hydroxide as a precursor thereof. Specific examples of the method for obtaining such particles include Patent Document 3.
- an oxidative roasting step (S2) may be performed.
- the nickel composite hydroxide obtained in the precursor crystallization step (S1) is oxidatively roasted to obtain a nickel composite oxide.
- a nickel composite oxide can be obtained by heat-treating in an oxygen-containing atmosphere and then cooling to room temperature.
- the roasting conditions in the oxidative roasting step (S2) are not particularly limited, and for example, roasting can be performed in an oxygen-containing atmosphere, an air atmosphere, at a temperature of 500 ° C. or higher and 700 ° C. or lower, for 1 hour or longer and 12 hours or shorter. preferable.
- the roasting temperature is 500 ° C. or higher
- the nickel composite hydroxide can be completely converted to the nickel composite oxide.
- the roasting temperature to 700 ° C. or lower, it is possible to prevent the specific surface area of the nickel composite oxide from becoming excessively small, which is preferable.
- the roasting time is preferably 12 hours or less.
- the oxygen concentration in the oxygen-containing atmosphere at the time of roasting is preferably equal to or higher than the oxygen concentration in air, that is, the oxygen concentration is preferably 20% by volume or higher. Since the oxygen atmosphere can be used, the upper limit of the oxygen concentration in the oxygen-containing atmosphere can be 100% by volume.
- the compound containing the element M cannot be co-precipitated in the crystallization step (S1), for example, the substance intended for the compound containing the element M with respect to the nickel composite hydroxide used in the oxidation roasting step S2. It may be added and baked so as to have the same amount ratio.
- the compound containing the element M to be added is not particularly limited, and for example, an oxide, a hydroxide, a carbonate, or a mixture thereof can be used.
- the oxidative roasting step (S2) if slight sintering is observed in the obtained nickel composite oxide after the completion of the oxidative roasting step (S2), a crushing treatment may be added.
- the oxidation roasting step (S2) at least a part of the nickel composite hydroxide may be converted to the nickel composite oxide, and not all the nickel composite hydroxide may be converted to the oxide.
- the mixing step (S10) is a step of mixing a nickel compound compound, a niobium compound, and a lithium compound to obtain a lithium mixture.
- niobium is solid-phase added by mixing the niobium compound in the mixing step (S10).
- the solid phase addition of niobium does not require a chemical solution as compared with the method of coprecipitating or coating niobium in a conventionally known crystallization step, so it is an addition method having a low environmental load and excellent productivity. be.
- the nickel composite compound is preferably at least one of a nickel composite hydroxide and a nickel composite oxide, and more preferably a nickel composite oxide. Further, the nickel composite compound is preferably obtained by a method including the above-mentioned crystallization step (S1) and / or oxidative roasting step (S2).
- niobium compound for example, niobium acid, niobium oxide, niobium nitrate, niobium pentachloride and the like can be used.
- niobium hydroxide or niobium oxide is preferable from the viewpoint of easy availability and avoiding contamination of calcined lithium-nickel composite oxide with impurities.
- the reactivity may change depending on the particle size of the added niobium compound.
- the particle size (D90) corresponding to the integrated volume fraction of 90% is preferably 0.1 ⁇ m or more and 20 ⁇ m or less, more preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and further. It is preferably 0.1 ⁇ m or more and 5 ⁇ m or less.
- the D90 of the niobium compound When the D90 of the niobium compound is larger than 20 ⁇ m, the reactivity at the time of firing may be lowered, the diffusion of niobium into the particles of the lithium nickel composite oxide may be insufficient, and the thermal stability may not be ensured. In addition, if the niobium D90 is too large, the formation of the coating layer 2 may be non-uniform.
- the particle size of the niobium compound can be appropriately adjusted within the range of the above particle size so that a positive electrode active material having desired characteristics can be obtained.
- the niobium compound D90 can be adjusted to the above range by crushing the raw material niobium compound using a crusher such as a ball mill, a planetary ball mill, a jet mill, a bead mill, or a pin mill. Further, if necessary, the class may be classified by a dry classifier or a sieving machine. The niobium compound D90 can be measured by a laser scattering diffraction method.
- the niobium compound is mixed in an amount having the desired niobium content with respect to the total number of atoms of Ni and element M contained in the nickel composite compound. Since the content of niobium does not change before and after the firing step, a niobium compound corresponding to the amount of niobium added to the positive electrode active material is added.
- the lithium compound is not particularly limited, and for example, lithium hydroxide, lithium nitrate, lithium carbonate, or a mixture thereof can be used.
- lithium hydroxide is preferably used from the viewpoint of having a low melting point and high reactivity.
- the lithium compound may be mixed, for example, in an amount such that the lithium content is 95 atomic% or more and 115 atomic% or less with respect to the total sum (Me) of Ni, the element M and Nb, and 98 atomic% or more. It may be mixed at 115 atomic% or less, or at 98 atomic% or more and 110 atomic% or less.
- the firing step (S20) is a step of firing the obtained lithium mixture to obtain particles 1 of the lithium nickel composite oxide.
- the firing conditions are not particularly limited, but for example, it is preferable to fire at a temperature of 700 ° C. or higher and 800 ° C. or lower and 1 hour or longer and 24 hours or lower in an oxygen-containing atmosphere. Further, after firing, the particles may be cooled to room temperature to obtain particles 1 of the lithium nickel composite oxide.
- the firing temperature is 700 ° C. or higher, the crystal structure of the particles 1 of the lithium nickel composite oxide can be sufficiently grown. Further, when the firing temperature is 800 ° C. or lower, it is possible to suppress the mixing of Ni atoms into the Li sites of the obtained lithium nickel composite oxide particles 1.
- the firing time is 1 hour or more because the temperature inside the firing container can be made uniform and the reaction can be made uniform. Further, even if the firing is performed for a longer time than 24 hours, no significant change is observed in the obtained lithium nickel composite oxide. Therefore, from the viewpoint of energy efficiency, the firing time is preferably 24 hours or less, preferably 12 hours. It may be less than or equal to, 10 hours or less, or 6 hours or less.
- the oxygen-containing atmosphere is preferably an atmosphere containing 80% by volume or more of oxygen. This is because it is preferable to set the oxygen concentration in the atmosphere to 80% by volume or more because it is possible to particularly suppress the mixing of Ni atoms with the Li sites in the obtained lithium nickel composite oxide. Since the oxygen atmosphere can be used, the upper limit of the oxygen concentration in the oxygen-containing atmosphere can be 100% by volume.
- the coating step (S30) is a step of adhering the coating liquid to the surface of the particles 1 of the obtained lithium nickel composite oxide to form the coating layer 2.
- the lithium nickel composite oxide particles 1 and the coating liquid are mixed and dried to form the coating layer 2 on the surface of the lithium nickel composite oxide particles 1.
- the heat treatment step (S40) may be optionally performed in an oxygen-containing atmosphere.
- an example of the coating step (S30) will be described.
- a predetermined amount of the coating liquid is prepared (coating agent preparation step).
- the coating agent depends on the content of the constituent elements (excluding Li and O) of the coating layer 2 per the specific surface area (m 2 / g) of the particles 1 of the lithium nickel composite oxide obtained in the firing step (S20). Can be prepared.
- the coating liquid contains at least one element selected from the group consisting of Al, Si, Ti, V, Ga, Ge, Zr, Nb, Mo, Ta and W.
- the coating liquid can be prepared by dissolving a raw material compound containing the constituent elements (excluding Li and O) of the target coating layer 2 in a solvent.
- Examples of the raw material compound include one or more selected from the group consisting of chelates using a complex having an alkoxide, a carbonyl group, a peroxy group, and the like.
- the coating liquid may be liquid at the time of adhering to the surface of the particles 1 of the lithium nickel composite oxide.
- a compound containing a constituent element of the coating layer 2 is dissolved in a solvent. It may be prepared and made liquid at room temperature, or it may be a compound containing a constituent element of the coating layer 2 having a low melting point and dissolved by a low temperature heat treatment.
- the coating liquid may or may not contain Li.
- the Li present in the particles 1 of the lithium nickel composite oxide in the coating step (S30) and / or the heat treatment step (S40) and the compound containing the above-mentioned constituent elements in the coating liquid Can react to form the coating layer 2.
- the coating liquid is attached to the surface of the lithium nickel composite oxide particles 1.
- the coating liquid may be attached, for example, by mixing the lithium nickel composite oxide particles 1 and the coating liquid (mixture preparation step).
- a general mixer can be used for mixing.
- drying may be performed after mixing (drying step).
- the coating layer 2 having a more uniform and specific thickness, it is preferable to proceed with the mixture preparation step and the drying step in parallel, and it is preferable to use a rolling flow coating device.
- the coating liquid causes shrinkage due to drying, a gap is formed in the coating layer 2 to be formed only by going through the mixture preparation step and the drying step once, respectively, and the particles 1 of the lithium nickel composite oxide and the solid electrolyte are formed. It may not be able to fully function to protect the contact. However, when the rolling flow coating device is used, the coating liquid is sprayed on the particles 1 of the lithium nickel composite oxide flowing by the air flow heated in the device, so that the mixture preparation step and the drying step are performed in parallel. This is preferable because a uniform coating layer without gaps can be obtained.
- the drying step it is preferable to perform drying at a temperature that can sufficiently remove the solvent and the like of the coating agent.
- the supply air temperature may be set to 80 ° C. or higher and lower than 300 ° C.
- additional drying may be performed separately with a stationary dryer.
- the atmosphere of the drying step is not particularly limited, but is inert such as air, nitrogen and argon gas supplied from a compressor equipped with a dryer in order to prevent the particles 1 of the lithium nickel composite oxide from reacting with the moisture in the atmosphere.
- the atmosphere is preferable.
- a heat treatment step (S40) may be provided in which the lithium nickel composite oxide particles 1 having the coating layer 2 formed on the surface are heat-treated at 300 ° C. or higher.
- the bond between the coating layer 2 and the particles 1 of the lithium nickel composite oxide can be further strengthened.
- the heat treatment conditions in the heat treatment step (S40) are not particularly limited, but it is preferable to perform the heat treatment in an oxygen-containing atmosphere at a temperature of 300 ° C. or higher and 600 ° C. or lower for 1 hour or longer and 5 hours or shorter.
- the oxygen-containing atmosphere may be, for example, an air atmosphere.
- the oxygen concentration in the oxygen-containing atmosphere in the heat treatment step (S40) is preferably equal to or higher than the oxygen concentration in the air atmosphere, that is, the oxygen concentration is preferably 20% by volume or more.
- the oxygen-containing atmosphere may be an oxygen atmosphere, and the upper limit of the oxygen concentration in the oxygen-containing atmosphere is 100% by volume.
- the heat treatment temperature is 300 ° C. or higher, impurities contained in the coating liquid can be further suppressed from remaining inside the positive electrode active material 10. Further, when the heat treatment temperature is 600 ° C. or lower, it is possible to suppress excessive diffusion of the components of the coating layer 2 and maintain the shape of the coating layer 2.
- the heat treatment time is 1 hour or more, it is possible to further suppress the impurities contained in the coating liquid from remaining inside the positive electrode active material 10. Further, even when the heat treatment time is longer than 5 hours, no significant change is observed in the obtained positive electrode active material 10. Therefore, from the viewpoint of energy efficiency, the heat treatment time is preferably 5 hours or less.
- the particles are cooled to room temperature to obtain a positive electrode active material having lithium nickel composite oxide particles 1 as a final product and a coating layer 2 on the surface thereof.
- the positive electrode active material 10 may be produced by carrying out the coating step (S30). This is because the coating layer can be uniformly and firmly formed on the surface of the particles of the lithium nickel composite oxide even when the heat treatment step (S40) is not performed. Even if the heat treatment step is not performed, it is preferable to perform drying in order to reduce or remove the solvent and water content of the coating agent, if necessary.
- All-solid-state lithium-ion secondary battery (hereinafter, also referred to as “all-solid-state battery”) according to the present embodiment includes a positive electrode, a negative electrode, and a solid electrolyte, and is described above.
- the positive electrode contains a positive electrode active material.
- the all-solid-state battery according to the present embodiment will be described for each component.
- the embodiments described below are merely examples, and the all-solid-state battery can be implemented in various modifications and improvements based on the knowledge of those skilled in the art, including the following embodiments. Further, the all-solid-state battery is not particularly limited in its use.
- the positive electrode can be formed by molding a positive electrode mixture.
- the positive electrode is appropriately processed according to the battery used. For example, in order to increase the electrode density, a pressure compression process or the like by a press or the like can be performed.
- the above-mentioned positive electrode mixture can be formed by mixing the above-mentioned positive electrode active material in powder form with a solid electrolyte.
- the solid electrolyte is added to give the electrode proper ionic conductivity.
- the material of the solid electrolyte is not particularly limited, but is, for example, a sulfide-based solid electrolyte such as Li 3 PS 4 , Li 7 P 3 S 11 , Li 10 GeP 2 S 12 , Li 7 La 3 Zr 2 O 12 , Li 0 .
- Oxide-based solid electrolytes such as .34 La 0.51 TiO 2.94 and polymer-based electrolytes such as PEO can be used.
- a binder or a conductive auxiliary agent can be added to the positive electrode mixture.
- the binder plays a role of binding the positive electrode active material.
- the binder used in the positive electrode mixture is not particularly limited, and for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluororubber, ethylenepropylenediene rubber, styrene-butadiene, cellulose resin, and polyacrylic acid.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- fluororubber fluororubber
- ethylenepropylenediene rubber styrene-butadiene
- cellulose resin cellulose resin
- polyacrylic acid polyacrylic acid
- the conductive material is added to give appropriate conductivity to the electrode.
- the material of the conductive material is not particularly limited, and for example, graphite such as natural graphite, artificial graphite and expanded graphite, and carbon black materials such as acetylene black and Ketjen black (registered trademark) can be used.
- the mixing ratio of each substance in the positive electrode mixture is not particularly limited.
- the content of the positive electrode active material of the positive electrode mixture can be 50 parts by mass or more and 90 parts by mass or less, and the content of the solid electrolyte can be 10 parts by mass or more and 50 parts by mass or less.
- the method for producing the positive electrode is not limited to the above-mentioned example, and other methods may be used.
- the negative electrode can be formed by molding a negative electrode mixture.
- the negative electrode is formed by substantially the same method as the above-mentioned positive electrode, although the components constituting the negative electrode mixture and the composition thereof are different, and various treatments are performed as necessary in the same manner as the positive electrode.
- the negative electrode mixture can be prepared by mixing the negative electrode active material and the solid electrolyte.
- the negative electrode active material for example, an occlusion material capable of storing and desorbing lithium ions can be adopted.
- the occluded substance is not particularly limited, but one or more selected from, for example, a calcined body of an organic compound such as natural graphite, artificial graphite, and a phenol resin, and a powdered body of a carbon substance such as coke can be used.
- a sulfide electrolyte such as Li 3 PS 4 can be used as the solid electrolyte as in the case of the positive electrode.
- the negative electrode may be a sheet-like member made of a substance containing a metal alloying with lithium such as metallic lithium and indium.
- the solid electrolyte is a solid having Li + ion conductivity.
- the solid electrolyte one selected from sulfides, oxides, polymers and the like can be used alone, or two or more thereof can be mixed and used.
- the sulfide-based solid electrolyte is not particularly limited, and any sulfide-based solid electrolyte that contains sulfur (S) and has lithium ion conductivity and electron insulating properties can be used.
- Examples of the sulfide-based solid electrolyte include Li 2 SP 2 S 5 , Li 2 S-SiS 2 , LiI-Li 2 S-SiS 2 , LiI-Li 2 SP 2 S 5 , LiI-Li 2 .
- the oxide-based solid electrolyte is not particularly limited, and can be used as long as it contains oxygen (O) and has lithium ion conductivity and electron insulation.
- oxide-based solid electrolyte examples include lithium phosphate (Li 3 PO 4 ), Li 3 PO 4 NX, LiBO 2 NX, LiNbO 3 , LiTaO 3 , Li 2 SiO 3 , Li 4 SiO 4 ⁇ Li 3 PO 4 .
- an electrolyte other than the above may be used, and for example, Li 3N, LiI, Li 3N - LiI - LiOH or the like may be used.
- the polymer-based solid electrolyte is not particularly limited as long as it is a polymer compound exhibiting ionic conductivity, and for example, polyethylene oxide, polypropylene oxide, copolymers thereof, and the like can be used. Further, the organic solid electrolyte may contain a supporting salt (lithium salt). When a solid electrolyte is used, the solid electrolyte may be mixed in the positive electrode material in order to ensure contact between the electrolyte and the positive electrode active material.
- the all-solid-state battery composed of the positive electrode, the negative electrode, and the solid electrolyte can have various shapes such as a coin shape and a laminated shape. Regardless of the shape, the positive electrode and the negative electrode can be laminated via the solid electrolyte. Then, the positive electrode current collector and the positive electrode terminal leading to the outside and the negative electrode current collector and the negative electrode terminal leading to the outside are connected by using a current collecting lead or the like, and sealed in a battery case. It can be an all-solid-state battery.
- the all-solid-state battery according to the embodiment of the present invention using the above-mentioned positive electrode active material exhibits high capacity.
- the positive electrode active material of the present embodiment is used as the positive electrode to form the test battery shown in FIG. 4, the current density is 0.2 mA / cm 2 , and the cutoff voltage is 4.3 V (vs. Li). ), And after a one-hour rest, the initial discharge capacity, which is the discharge capacity when the cutoff voltage is discharged to 2.5 V (vs. Li), is preferably 130 mAh / g or more.
- Example 1 1. Production of Lithium-Nickel Composite Oxide Lithium-nickel composite oxide was produced by the following steps.
- (A) Crystallization step The temperature in the tank was maintained at 50 ° C. while stirring with 10 L of pure water in a reaction tank having an internal volume of 60 L. At this time, the inside of the reaction vessel had a nitrogen atmosphere in which the oxygen concentration was 1% by volume or less. An appropriate amount of 25% by mass sodium hydroxide aqueous solution and 25% by mass ammonia water were added to the reaction vessel to bring the pH value based on the liquid temperature to 25 ° C to 12.8 and the ammonia concentration of the solution in the reaction vessel to 15 g / L. The initial aqueous solution was prepared so as to be.
- the pH of the reaction aqueous solution in the reaction tank was improved until it reached 13.0 based on the liquid temperature of 25 ° C. This operation is intended to precipitate nickel ions that are complexed with ammonia and dissolved in the liquid phase on the hydroxide to obtain the desired chemical composition.
- reaction aqueous solution was solid-liquid separated by a Buchner funnel, a filter can, and a vacuum pump vacuum filter. Further, the operation of dispersing the obtained solid phase in 20 L of pure water at 40 ° C. and solid-liquid separation was repeated twice to remove water-soluble impurities such as sodium sulfate from the nickel composite hydroxide.
- the cake-like solid phase after solid-liquid separation after washing is dried in a stationary dryer at 120 ° C. for 24 hours in an air atmosphere, and then subjected to a flue with an opening of 100 ⁇ m to obtain a powdery nickel composite hydroxide. rice field.
- (C) Mixing step Mitsuwa Chemicals so that the amount of substance of Nb in the nickel composite oxide is 0.1% of the total amount of substances of Ni, Co, and Al contained in the nickel composite oxide.
- Niobic acid (Nb 2 O 3 ⁇ xH 2 O) powder manufactured by Co., Ltd. was added and weighed so that the amount of substance of Li was 103% of the total amount of substance of Ni, Co, Al and Nb.
- Lithium monohydrate was added and mixed using a Turbler Shaker Mixer (manufactured by Dalton Co., Ltd., T2F) to obtain a lithium mixture.
- (E) Particle size distribution The particle size distribution of the lithium nickel composite oxide was measured using a laser diffraction / scattering type particle size distribution measuring device (Microtrac HRA, manufactured by Nikkiso Co., Ltd.). From the results, it was confirmed that the volume-based average particle size D50 was 5.4 ⁇ m, and the variation index ((D90-D10) / MV) calculated from D10, D90, and MV was 0.44.
- lithium nickel composite oxide 500 g was flowed into the chamber with air heated to 120 ° C. and a flow rate of 0.3 m 3 / h, and a coating liquid was applied to the lithium nickel composite oxide at 1.7 ml / min. Sprayed.
- the lithium nickel composite oxide was recovered from the chamber and heat-treated at 400 ° C. for 10 hours using an atmosphere firing furnace (BM-50100M manufactured by Siliconit Co., Ltd.). Then, the mixture was cooled to room temperature to obtain particles (positive electrode active material) of a lithium nickel composite oxide having a coating layer (including Li and Ti).
- test battery A battery having the structure shown in FIG. 4 (hereinafter referred to as “test battery”) was used for evaluating the capacity of the obtained positive electrode active material.
- the test battery SBA includes a case having a negative electrode can NC and a positive electrode can PC, and a green compact cell C housed in the case.
- the case has a negative electrode can NC that is hollow and has one end open, and a positive electrode can PC that is arranged at the opening of the negative electrode can NC. Further, a space for accommodating the green compact cell C is formed between the positive electrode can PC and the negative electrode can NC.
- the positive electrode can PC is fixed to the negative electrode can NC, for example, with a thumbscrew SW. Further, the negative electrode can NC has a negative electrode terminal, and the positive electrode can PC has a positive electrode terminal.
- the case also has an insulating sleeve ISV. The insulating sleeve ISV is fixed between the negative electrode can NC and the positive electrode can PC so as to maintain a non-contact state.
- a pressure screw PSW is provided at one closed end of the negative electrode can NC. After fixing the positive electrode can PC to the negative electrode can NC, the pressure screw PSW is tightened toward the accommodation space of the powder cell C. By squeezing, the green compact cell C is held in a pressurized state through the hemispherical washer W. Further, a screw-in type plug P is provided at one end of the negative electrode can NC where the pressure screw PSW exists. An Oling OL is provided between the negative electrode can NC and the positive electrode can PC, and between the negative electrode can NC and the plug P, and the gap between the negative electrode can NC and the positive electrode can PC is sealed, and the inside of the case is sealed. Airtightness is maintained.
- the green compact cell C is a pellet in which the positive electrode layer PL, the solid electrolyte layer SEL, and the negative electrode layer NL are laminated in this order.
- the positive electrode layer PL comes into contact with the inner surface of the positive electrode can PC through the lower current collector LCC.
- the negative electrode layer NL contacts the inner surface of the negative electrode can NC through the upper current collector UCC, the hemispherical washer W and the pressure screw PSW.
- the lower current collector LCC, the powder compact cell C, and the upper current collector UCC are protected by the sleeve SV from electrical contact between the positive electrode layer PL and the negative electrode layer NL.
- test battery SBA (Manufacturing of evaluation battery) The test battery SBA was prepared as follows.
- the lower current collector LCC, the pellet with the positive electrode layer PL arranged downward, the indium (In) foil (negative electrode layer NL), and the upper current collector UCC are laminated in this order, pressurized with 9 kN, and the electrode (compactor).
- Body cell C) was constructed.
- the electrode (compact cell C) was sealed in the case, and the pressure screw was tightened with a torque of 6 to 7 Nm.
- the test battery SBA was prepared in a glove box having an Ar atmosphere with a dew point controlled at ⁇ 80 ° C.
- the initial discharge capacity is the current density with respect to the positive electrode after the open circuit voltage OCV (Open Circuit Voltage) is stabilized by leaving it for about 24 hours after manufacturing a test battery using an indium foil for the negative electrode.
- OCV Open Circuit Voltage
- the battery is charged to a cutoff voltage of 3.7 V (vs. Li-In) at 0.2 mA / cm 2 and discharged to a cutoff voltage of 1.9 V (vs. Li-In) after a one-hour rest. It was evaluated by measuring the discharge capacity (initial discharge capacity). The measurement result was 134 mAh / g.
- Example 2 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 1 except that the amount of Nb added in the lithium-nickel composite oxide synthesis step of Example 1 was 0.8%. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 3 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 1 except that the amount of Nb added in the lithium-nickel composite oxide synthesis step of Example 1 was 1.2%. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 4 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 1 except that the amount of Nb added in the lithium-nickel composite oxide synthesis step of Example 1 was set to 3%. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 5 The coated lithium nickel composite oxide was synthesized under the same conditions as in Example 2 except that the firing time in the lithium nickel composite oxide synthesis step of Example 2 was set to 12 hours.
- the manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 6 The coated lithium nickel composite oxide was synthesized under the same conditions as in Example 3 except that the firing time in the lithium nickel composite oxide synthesis step of Example 3 was set to 12 hours.
- the manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 7 The lithium nickel composite oxide obtained in Example 2 was coated with lithium niobate in the coating step and heat-treated under the following conditions, but the coated lithium nickel composite oxide was coated under the same conditions as in Example 2. Was synthesized. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- the lithium nickel composite oxide was recovered from the chamber and heat-treated at 350 ° C. for 1 hour under an atmospheric firing furnace (BM-50100M manufactured by Siliconit Co., Ltd.). Then, the mixture was cooled to room temperature to obtain particles (positive electrode active material) of a lithium nickel composite oxide having a coating layer (including Li and Nb).
- Example 8 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 6 except that the proportion a of Li in the lithium-nickel composite oxide synthesis step of Example 6 was set to 1.00.
- the manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 9 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 6 except that the proportion a of Li in the lithium-nickel composite oxide synthesis step of Example 6 was 1.09. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 10 Covered under the same conditions as in Example 6 except that the proportion of Ni (1-xy) in the lithium-nickel composite oxide synthesis step of Example 6 was 0.85 and the proportion of Co (x 1 ) was 0.116. A lithium nickel composite oxide was synthesized. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 11 Covered under the same conditions as in Example 6 except that the proportion of Ni (1-xy) in the lithium-nickel composite oxide synthesis step of Example 6 was 0.744 and the proportion of Co (x 1 ) was 0.222. A lithium nickel composite oxide was synthesized. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 1 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 1 except that Nb was not added in the lithium-nickel composite oxide synthesis step of Example 1. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Comparative Example 2 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Comparative Example 1 except that the firing temperature in the lithium-nickel composite oxide synthesis step of Comparative Example 1 was set to 735 ° C. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 3 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 1 except that the amount of Nb added in the lithium-nickel composite oxide synthesis step of Example 1 was 5 atomic%. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 4 The coated lithium nickel composite oxide was synthesized under the same conditions as in Example 2 except that the particles of the lithium nickel composite oxide of Example 2 were not coated. The manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- Example 5 A coated lithium-nickel composite oxide was synthesized under the same conditions as in Example 6 except that the proportion a of Li in the lithium-nickel composite oxide synthesis step of Example 6 was 1.18.
- the manufacturing conditions are shown in Table 1 and the results are shown in Table 2.
- the discharge capacity in the all-solid-state battery was significantly improved as compared with the positive electrode active material of Comparative Example 1 containing no Nb.
- the discharge capacity was significantly improved.
- the characteristics of the positive electrode active material such as crystallite diameter and specific surface area
- the battery characteristics are also about the same, and it has been shown that a positive electrode active material having high battery characteristics can be obtained even if the firing time is 5 hours. Further, it was shown that even in Example 7 in which the coating layer contains Nb, the coating layer has a high discharge capacity as in Examples 1 to 6 in which Ti is contained.
- Example 8 in which the Li ratio (a) is 1.00 and Example 9 in which the Li ratio (a) is 1.09, the discharge is as high as that in Example 6 (a: 1.04). It was shown to have capacity. Further, Example 10 (Ni ratio: 0.850) and Example 11 (Ni ratio: Ni) have different Ni ratios (1-xy) from those of Example 6 (Ni ratio: 0.806). From 0.744), it is clear that the higher the proportion of Ni, the higher the discharge capacity.
- a positive electrode active material that can be suitably used for a positive electrode of an all-solid-state lithium ion secondary battery that requires a high battery capacity, and a method for producing the same.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
まず、本実施形態に係る全固体リチウムイオン二次電池用正極活物質(以下、「正極活物質」ともいう。)の一構成例について説明する。
リチウムニッケル複合酸化物の粒子1は、空間群R-3mに属する結晶構造を有し、少なくともリチウム(Li)、ニッケル(Ni)、元素M、及びNbを含む複合酸化物である。
リチウムニッケル複合酸化物の粒子1に含まれる各元素の物質量比(モル比)をLi:Ni:M:Nb=a:(1-x-y):x:yで表した場合、0.98≦a≦1.15、0<x≦0.5、0<y≦0.03、0<x+y≦0.5を満たす。また、上記物質量比において、0.98≦a≦1.15、0<x≦0.3、0<y≦0.02、0<x+y≦0.4を満たすことが好ましい。
リチウムニッケル複合酸化物の粒子1は、空間群R-3mに属する結晶構造を有する。リチウムニッケル複合酸化物の粒子1が空間群R-3mに属する結晶構造を有する場合、二次電池において、内部抵抗の上昇を抑制することができる。
リチウムニッケル複合酸化物の粒子1は、結晶子径が140nm以下であることが好ましく、40nm以上140nm以下であることがより好ましい。また、結晶子径の上限を含む範囲は、130nm以下であってもよい。また、結晶子径の下限を含む範囲は、50nm以上であってもよい。なお、結晶子径は、上記のXRD回折パターンの(003)に帰属するピークを用い、シェラー法により算出することができる。リチウムニッケル複合酸化物の粒子1の結晶子径が140nmを超える場合、結晶内の固体内拡散距離が長くなり電池容量が低下することがある。また、リチウムニッケル複合酸化物の粒子1の結晶子径が40nm未満である場合、結晶構造が不安定になり、電池容量が低下しやすい。
リチウムニッケル複合酸化物の粒子1は、粒子1の全量に対して、中和滴定により求められる溶出リチウムイオン量が0.30質量%以上1.00質量%以下であり、0.30質量%以上0.70質量%以下であることが好ましい。なお、溶出リチウムイオン量は、リチウムニッケル複合酸化物の粒子1を水に分散させた際に、水に溶出するリチウムイオン量を、塩酸を用いた中和滴定法により求めることができる。中和滴定法としては、Warder法や、Winkler法を用いることができる。
さらに、リチウムニッケル複合酸化物の粒子1は、結晶子径が140nm以下であり、かつ、溶出リチウムイオン量が0.30質量%以上であることが好ましい。
リチウムニッケル複合酸化物の粒子1は、複数の一次粒子が凝集して構成された二次粒子を含む。また、リチウムニッケル複合酸化物の粒子1は、単独の一次粒子を含んでもよく、単独の一次粒子と二次粒子との混合物であってもよい。
リチウムニッケル複合酸化物の粒子1は、粒度分布の積算体積分布曲線において積算体積率50%に相当する粒径(D50、以下、「平均粒径D50」ともいう。)が7μm以下であることが好ましく、2μm以上7μm以下であることがより好ましく、3μm以上7μm以下であることがさらに好ましい。なお、平均粒径(D50)は、レーザー光回折散乱式の粒度分布計で計測することができる。
リチウムニッケル複合酸化物の粒子1の粒度分布の広がりを示す指標である[(d90-d10)/体積平均粒径Mv]は、特に限定されないが、粒子径を均一化するという観点から、0.7以下であってもよく、0.6以下であってもよく、0.55以下であってもよい。粒子径が比較的に均一である場合、被覆層2を、リチウムニッケル複合酸化物の粒子1の表面に均一に被覆することが容易となり、二次電池において良好な出力特性を有することができる。なお、[(d90-d10)/体積平均粒径Mv]の下限は特に限定されないが、例えば、0.3以上である。また、[(d90-d10)/体積平均粒径Mv]は、充填性の観点から、0.7以上であってもよく、後述する正極活物質の製造方法を用いることにより、比較的均一に被覆層2を被覆することができる。
リチウムニッケル複合酸化物の粒子1の比表面積は、特に限定されず、例えば、0.3m2/g以上2.0m2/g以下であってもよく、0.3m2/g以上1.0m2/g以下であってもよい。比表面積が上記範囲である場合、出力特性が良好である。なお、比表面積は、窒素吸着BET法により測定することができる。
正極活物質10は、リチウムニッケル複合酸化物の粒子1の表面に被覆層2を備える。粒子1の表面に被覆層2を有することにより、正極活物質10を含む正極を備えた二次電池において、正極活物質10と固体電解質との相互反応を抑制できる。
被覆層2の被覆量は特に限定されないが、被覆されるリチウムニッケル複合酸化物の粒子1の比表面積(m2/g)に応じて、被覆量を調整することができる。被覆層2は、例えば、リチウムニッケル複合酸化物の粒子1の表面積1m2当り、好ましくは30μmol以上600μmol以下、より好ましくは50μmol以上400μmol以下の割合で被覆層2の構成元素(Li及びOを除く)を含有することがより好ましい。
被覆層の平均厚さは、例えば、2nm以上20nm以下であることが好ましく、2nm以上15nm以下であることがより好ましく、5nm以上15nm以下であることがさらに好ましい。
また、被覆層2は、リチウムニッケル複合酸化物の粒子1の表面に隣接して存在することが好ましい。被覆層2が粒子1の表面に隣接して存在するか否かは、被覆層2の構成元素を含む化合物が、リチウムニッケル複合酸化物の粒子1の表面から遊離して存在するか否かで判断できる。被覆層2がリチウムニッケル複合酸化物の粒子1の表面から遊離する場合は、電気化学的に電池容量には寄与しないので、重量当たりの電池容量を下げる要因となる。
次に、本実施形態に係る全固体リチウムイオン二次電池用正極活物質(以下、「正極活物質」ともいう。)の製造方法について説明する。本実施形態の製造方法を用いることにより、上記の正極活物質10を生産性高く製造することができる。
晶析工程(S1)では、リチウムニッケル複合酸化物の前駆体であるニッケル複合水酸化物を晶析反応により調製する。
前駆体晶析工程(S1)の後に、酸化焙焼工程(S2)を行ってもよい。酸化焙焼工程(S2)では、前駆体晶析工程(S1)で得られたニッケル複合水酸化物を酸化焙焼して、ニッケル複合酸化物を得る。酸化焙焼工程(S2)では、酸素含有雰囲気中で熱処理し、その後、室温まで冷却することで、ニッケル複合酸化物を得ることができる。
混合工程(S10)は、ニッケル複合化合物と、ニオブ化合物と、リチウム化合物とを混合して、リチウム混合物を得る工程である。
焼成工程(S20)は、得られたリチウム混合物を焼成して、リチウムニッケル複合酸化物の粒子1を得る工程である。焼成条件は特に限定されないが、例えば、酸素含有雰囲気中で700℃以上800℃以下の温度、1時間以上24時間以下で焼成することが好ましい。また、焼成後、室温まで冷却して、リチウムニッケル複合酸化物の粒子1を得てもよい。
被覆工程(S30)は、得られたリチウムニッケル複合酸化物の粒子1の表面に、被覆液を付着させて、被覆層2を形成する工程である。
さらに、必要に応じて被覆工程(S30)の後に、被覆層2が表面に形成されたリチウムニッケル複合酸化物の粒子1を、300℃以上で熱処理する熱処理工程(S40)を備えてもよい。熱処理工程(S40)により、被覆層2とリチウムニッケル複合酸化物の粒子1との結合をより強固にすることができる。
本実施形態に係る全固体リチウムイオン二次電池(以下、「全固体電池」ともいう。)は、正極と、負極と、固体電解質とを備え、上記の正極活物質を正極に含む。以下、本実施形態に係る全固体電池について、構成要素ごとにそれぞれ説明する。
正極は、正極合剤を成型し、形成することができる。なお、正極は、使用する電池にあわせて適宜処理される。たとえば、電極密度を高めるためにプレスなどによる加圧圧縮処理等を行うこともできる。
その固体電解質の材料は特に限定されないが、例えばLi3PS4、Li7P3S11、Li10GeP2S12などの硫化物系固体電解質や、Li7La3Zr2O12、Li0.34La0.51TiO2.94などの酸化物系固体電解質やPEOなどのポリマー系電解質を用いることができる。
負極は、負極合剤を成型し、形成することができる。
負極は、負極合剤を構成する成分やその配合等は異なるものの、実質的に上述の正極と同様の方法によって形成され、正極と同様に必要に応じて各種処理が行われる。
固体電解質は、Li+イオン伝導性を持つ固体である。固体電解質としては、硫化物、酸化物、ポリマーなどから選ばれる1種を単独で、あるいは2種類以上を混合して用いることができる。
次に、本実施形態に係る全固体電池の部材の配置、構成の例について説明する。
上記の正極、負極および固体電解質で構成される全固体電池は、コイン形や積層形など、種々の形状にすることができる。いずれの形状をとる場合であっても、正極および負極を、固体電解質を介して積層させることができる。そして、正極集電体と外部に通ずる正極端子との間、および、負極集電体と外部に通じる負極端子との間を、集電用リードなどを用いて接続し、電池ケースに密閉して全固体電池とすることができる。
上述の正極活物質を用いた本発明の一実施形態に係る全固体電池は、高容量を発現する。
具体的には、本実施形態の正極活物質を正極に用いて、図4に示す試験用電池を構成し、電流密度を0.2mA/cm2として、カットオフ電圧4.3V(vs.Li)まで充電し、1時間の休止後、カットオフ電圧2.5V(vs.Li)まで放電した場合の放電容量である、初期放電容量が130mAh/g以上であることが好ましい。
1.リチウムニッケル複合酸化物の製造
以下の工程により、リチウムニッケル複合酸化物の製造を行った。
内容積60Lの反応槽内に、10Lの純水を入れて撹拌しながら、槽内温度を50℃に維持した。このときの反応槽内は、酸素濃度が1容量%以下である窒素雰囲気とした。
この反応槽内に、25質量%水酸化ナトリウム水溶液と25質量%アンモニア水を適量加えて、液温25℃基準のpH値が12.8に、反応槽内溶液のアンモニア濃度が15g/Lとなるように初期水溶液を調製した。
洗浄を終えた固液分離後のケーキ状の固相を、120℃の定置型乾燥機で24時間、空気雰囲気下で乾燥後、目開き100μmのフルイにかけて粉末状のニッケル複合水酸化物を得た。
雰囲気焼成炉(株式会社シリコニット製、BM-50100M)を用いて、作製した複合水酸化物を酸素濃度が20体積%である空気雰囲気下、600℃、2時間焼成した後、室温まで冷却し、ニッケル複合酸化物を得た。
ニッケル複合酸化物に、このニッケル複合酸化物に含まれるNi、Co、Alの物質量の総和に対して、Nbの物質量が0.1%となるように三津和化学薬品株式会社製のニオブ酸(Nb2O3・xH2O)粉末を添加し、Ni、Co、Al、Nbの総物質量に対してLiの物質量が103%となるように秤量した水酸化リチウム一水和物を加えて、ターブラーシェーカーミキサー(株式会社ダルトン製、T2F)を用いて混合し、リチウム混合物を得た。
雰囲気焼成炉(株式会社シリコニット製、BM-50100M)を用いて、得られたリチウム混合物を、酸素濃度が90体積%以上の酸素含有雰囲気中にて750℃で、5時間焼成した後、室温まで冷却した。これにより、リチウムニッケル複合酸化物の粒子を得た。
得られたリチウムニッケル複合酸化物に対して、以下の評価を行った。
ICP発光分光分析器(VARIAN社製、725ES)を用いた分析により、リチウムニッケル複合酸化物は、Li、Ni、Co、Al、Nbの物質量比が、Li:Ni:Co:Al:Nb=1.04:0.815:0.150:0.034:0.001であることを確認した。
リチウムニッケル複合酸化物の粒子の結晶構造を、XRD(PANALYTICAL社製、X‘Pert、PROMRD)を用いて測定したところ、回折パターンにR-3m構造に帰属されるピークが検出される層状岩塩型の結晶構造であることが確認された。
また、回折パターン中(003)面帰属ピークの半価幅を計測し、シェラー法を用いて結晶子の大きさを算出すると、123.4nmであることが確認された。
リチウムニッケル複合酸化物中の溶出リチウムイオン量を滴定法により求めた。リチウムニッケル複合酸化物2.0gを、125mlの純粋に分散させ、さらに塩化バリウム10%溶液2mLを加えた。撹拌をしながら1mol/L塩酸で中和滴定を行い、得られた滴定曲線のpH4付近の変曲点までに要した1mol/L塩酸の量を、溶出リチウムイオンに起因するLi量として換算した。その結果、リチウムニッケル複合酸化物中の溶出リチウムイオン量は0.31wt%であった。
リチウムニッケル複合酸化物のBET比表面積を、全自動BET比表面積測定装置(株式会社マウンテック製、マックソーブ)を用いて測定し、0.49m2/gであることを確認した。
リチウムニッケル複合酸化物の粒度分布を、レーザー回折散乱式粒度分布測定装置(日機装株式会社製、マイクロトラックHRA)を用いて測定した。その結果から体積基準の平均粒径D50は5.4μm、D10、D90、MVから算出されるばらつき指数((D90-D10)/MV)は、0.44であることを確認した。
得られたリチウムニッケル複合酸化物に対して、以下の被覆工程を実施した。
イソプロピルアルコール(IPA)30ml、チタンテトラブトキシド(Ti-BuOH)1.8gを添加して攪拌した溶液に、IPA20ml、アセチルアセトン0.9gを添加した溶液を、60℃で加熱攪拌しながら滴下した。これは高濃度のアセチルアセトンを、Ti溶液を直接添加しないためである。その後、IPA10mlに純水0.54gを添加したものを、冷却した前述の溶液へ添加した。最後に、得られた溶液にIPA65mlを加えて、被覆液を調整した。
(a)組成
ICP発光分光分析器(VARIAN社製、725ES)を用いた分析により、被覆リチウムニッケル複合酸化物は、0.88wt%のTiを含み、母材の単位面積当たりのTi量は370μmol/m2と確認された。
クライオイオンスライサ(JEOL, IB-09060CIS)で薄片化した被覆リチウムニッケル複合酸化物をTEM(JEOL製、JEM-ARM200F)で観察した結果、被覆層の厚みは11nmであることを確認した。
得られた正極活物質の容量の評価には、図4に示す構造の電池(以下、「試験用電池」という)を使用した。
図4に示すように、試験用電池SBAは、負極缶NC及び正極缶PCを有するケースと、ケース内に収容される圧粉体セルCとを備える。
試験用電池SBAは、以下のように作製した
作製した試験用電池の性能を示す充放電容量、以下のように評価した。
初期放電容量は、負極にインジウム箔を用いた試験用電池を製作してから24時間程度放置し、開回路電圧OCV(Open Circuit Voltage)が安定した後、正極に対する電流密度を0.2 mA/cm2としてカットオフ電圧3.7V(vs.Li-In)まで充電し、1時間の休止後、カットオフ電圧1.9V(vs.Li-In)まで放電したときの放電容量(初期放電容量)を測定することにより評価した。測定結果は134mAh/gであった。
実施例1のリチウムニッケル複合酸化物合成工程におけるNb添加量を0.8%にした以外は実施例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例1のリチウムニッケル複合酸化物合成工程におけるNb添加量を1.2%にした以外は実施例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例1のリチウムニッケル複合酸化物合成工程におけるNb添加量を3%にした以外は実施例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例2のリチウムニッケル複合酸化物合成工程における焼成時間を12hにした以外は実施例2と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例3のリチウムニッケル複合酸化物合成工程における焼成時間を12hにした以外は実施例3と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例2で得られたリチウムニッケル複合酸化物に対して、被覆工程でニオブ酸リチウムを被覆し、以下の条件で熱処理を行なった以外は、実施例2と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例6のリチウムニッケル複合酸化物合成工程におけるLiの割合aを1.00とした以外は実施例6と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例6のリチウムニッケル複合酸化物合成工程におけるLiの割合aを1.09とした以外は実施例6と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例6のリチウムニッケル複合酸化物合成工程におけるNiの割合(1-x-y)を0.85、Coの割合(x1)を0.116とした以外は実施例6と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例6のリチウムニッケル複合酸化物合成工程におけるNiの割合(1-x-y)を0.744、Coの割合(x1)を0.222とした以外は実施例6と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例1のリチウムニッケル複合酸化物合成工程におけるNbを無添加とした以外は実施例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
比較例1のリチウムニッケル複合酸化物合成工程における焼成温度を735℃にした以外は比較例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例1のリチウムニッケル複合酸化物合成工程におけるNb添加量を5原子%にした以外は実施例1と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例2のリチウムニッケル複合酸化物の粒子への被覆を行わなかった以外は実施例2と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例6のリチウムニッケル複合酸化物合成工程におけるLiの割合aを1.18とした以外は実施例6と同じ条件で被覆リチウムニッケル複合酸化物を合成した。製造条件を表1に、結果を表2に示す。
実施例の正極活物質では、Nbを含まない比較例1の正極活物質と比較して、全固体電池における放電容量が顕著に向上した。特に、実施例2(Nb:0.8原子%)では、顕著に放電容量が向上した。また、焼成時間が5時間である実施例1、2の正極活物質と焼成時間が12時間である実施例4、5の正極活物質では、結晶子径、比表面積などの正極活物質の特性や、電池特性(初期放電容量)も同程度であり、焼成時間が5時間でも高い電池特性を有する正極活物質を得ることができることが示されている。また、被覆層がNbを含む実施例7でも、被覆層がTiを含む実施例1~6と同様に、高い放電容量を有することが示された。
2…被覆層
10…正極活物質
SBA…試験用電池
PC…正極缶
NC…負極缶
ISV…絶縁スリーブ
C…圧粉体セル
PL…正極層
NL…負極層
SEL…固体電解質層
LCC…下部集電体
UCC…上部集電体
P…プラグ
PSW…加圧ネジ
W…半球座金
OL…オーリング
SV…スリーブ
SW…ネジ
N…ナット
Claims (8)
- リチウムニッケル複合酸化物の粒子と、前記粒子の表面を被覆する被覆層と、を有する全固体リチウムイオン二次電池用正極活物質であって、
前記リチウムニッケル複合酸化物の粒子は、
空間群R-3mに属する結晶構造を有し、
少なくともLi、Ni、元素MおよびNbを含み、
前記各元素の物質量比がLi:Ni:M:Nb=a:(1-x-y):x:y
(0.98≦a≦1.15、
0<x≦0.5、
0<y≦0.03、
0<x+y≦0.5、
前記元素Mは、Co、Al、Mn、Zr、Si、Zn及びTiからなる群より選択される少なくとも一種)で表され、
XRDで測定される(003)面に帰属される回折ピークからシェラー法により算出される結晶子径が140nm以下であり、
中和滴定により求められる溶出リチウムイオン量が、前記リチウムニッケル複合酸化物の粒子の全量に対して、0.30質量%以上1.00質量%以下であり、
前記被覆層は、
Liと、Al、Si、Ti、V、Ga、Ge、Zr、Nb、Mo、Ta及びWからなる群から選択される少なくとも1種の元素と、を含む複合酸化物である、
全固体リチウムイオン二次電池用正極活物質。 - 前記リチウムニッケル複合酸化物の粒子は、
複数の一次粒子が凝集して構成された二次粒子を含み、
前記二次粒子中に前記一次粒子の存在しない空隙部分を複数有する多孔質構造を有し、
窒素吸着BET法により測定した比表面積が0.3m2/g以上2.0m2/g以下である、
請求項1に記載の全固体リチウムイオン二次電池用正極活物質。 - 前記リチウムニッケル複合酸化物の粒子に含まれるニオブの少なくとも一部は、前記一次粒子の界面に偏析する、請求項2に記載の全固体リチウムイオン二次電池用正極活物質。
- 前記リチウムニッケル複合酸化物の粒子は、粒度分布の積算体積分布曲線において積算体積率50%に相当する粒径(D50)が7μm以下である、請求項1~3のいずれか一項に記載の全固体リチウムイオン二次電池用正極活物質。
- 前記被覆層の平均厚さは、2nm以上15nm以下である、請求項1~4のいずれか一項に記載の全固体リチウムイオン二次電池用正極活物質。
- ニッケル複合化合物と、ニオブ化合物と、リチウム化合物とを混合して混合物を得る混合工程と、
前記混合物を焼成して前記リチウムニッケル複合酸化物の粒子を得る焼成工程と、
前記リチウムニッケル複合酸化物の粒子の表面に、Al、Si、Ti、V、Ga、Ge、Zr、Nb、Mo、Ta及びWからなる群から選択される少なくとも1種の元素を含む被覆液を付着させ、前記被覆層を形成する被覆工程と、を備える、
請求項1~5のいずれか一項に記載の全固体リチウムイオン二次電池用正極活物質の製造方法。 - 前記ニッケル複合化合物は、ニッケル複合酸化物を含み、
晶析反応により調整されたニッケル複合水酸化物を酸化焙焼して前記ニッケル複合酸化物を得る酸化焙焼工程を備える、請求項6に記載の全固体リチウムイオン二次電池用正極活物質の製造方法。 - 前記被覆工程の後に、前記被覆層が表面に形成された前記リチウムニッケル複合酸化物の粒子を、300℃以上で熱処理する熱処理工程を備える、請求項6又は請求項7に記載の全固体リチウムイオン二次電池用正極活物質の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2022539579A JPWO2022025212A1 (ja) | 2020-07-30 | 2021-07-29 | |
CN202180059735.XA CN116157936A (zh) | 2020-07-30 | 2021-07-29 | 全固体锂离子二次电池用正极活性物质及其制造方法 |
US18/018,166 US20230268500A1 (en) | 2020-07-30 | 2021-07-29 | Positive electrode active material for all-solid-state lithium ion secondary battery and method for manufacturing the same |
EP21851567.4A EP4191703A1 (en) | 2020-07-30 | 2021-07-29 | Positive electrode active material for all-solid-state lithium ion secondary batteries, and method for producing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020129024 | 2020-07-30 | ||
JP2020-129024 | 2020-07-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022025212A1 true WO2022025212A1 (ja) | 2022-02-03 |
Family
ID=80036365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/028186 WO2022025212A1 (ja) | 2020-07-30 | 2021-07-29 | 全固体リチウムイオン二次電池用正極活物質とその製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20230268500A1 (ja) |
EP (1) | EP4191703A1 (ja) |
JP (1) | JPWO2022025212A1 (ja) |
CN (1) | CN116157936A (ja) |
WO (1) | WO2022025212A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023181452A1 (ja) * | 2022-03-24 | 2023-09-28 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、リチウムイオン電池、全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池、リチウムイオン電池用正極活物質の製造方法及び全固体リチウムイオン電池用正極活物質の製造方法 |
WO2023228958A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228957A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228956A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228959A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023238581A1 (ja) * | 2022-06-10 | 2023-12-14 | パナソニックホールディングス株式会社 | 被覆活物質、電極材料および電池 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010170715A (ja) | 2009-01-20 | 2010-08-05 | Toyota Motor Corp | 正極活物質材料 |
JP2011116580A (ja) | 2009-12-02 | 2011-06-16 | Sumitomo Metal Mining Co Ltd | ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 |
JP2014056661A (ja) | 2012-09-11 | 2014-03-27 | Toyota Motor Corp | 硫化物固体電解質 |
JP2015122298A (ja) * | 2013-11-22 | 2015-07-02 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質の製造方法、非水系電解質二次電池用正極活物質及びこれを用いた非水系電解質二次電池 |
JP2016076470A (ja) * | 2014-10-06 | 2016-05-12 | 日立金属株式会社 | リチウムイオン二次電池用正極活物質、それを用いたリチウムイオン二次電池用正極及びリチウムイオン二次電池 |
JP2019139854A (ja) * | 2018-02-06 | 2019-08-22 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法、非水系電解質二次電池用正極活物質の評価方法、および非水系電解質二次電池 |
JP2020087822A (ja) * | 2018-11-29 | 2020-06-04 | 住友金属鉱山株式会社 | リチウムニッケル含有複合酸化物とその製造方法、および、該リチウムニッケル含有複合酸化物を母材として用いたリチウムイオン二次電池用正極活物質とその製造方法 |
JP2020100541A (ja) * | 2018-12-20 | 2020-07-02 | 住友化学株式会社 | リチウム金属複合酸化物粉末、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池 |
JP2020129024A (ja) | 2019-02-07 | 2020-08-27 | コニカミノルタ株式会社 | 画像形成システム及び画像形成方法 |
JP2020167136A (ja) * | 2019-03-28 | 2020-10-08 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池 |
-
2021
- 2021-07-29 US US18/018,166 patent/US20230268500A1/en active Pending
- 2021-07-29 CN CN202180059735.XA patent/CN116157936A/zh active Pending
- 2021-07-29 JP JP2022539579A patent/JPWO2022025212A1/ja active Pending
- 2021-07-29 WO PCT/JP2021/028186 patent/WO2022025212A1/ja active Application Filing
- 2021-07-29 EP EP21851567.4A patent/EP4191703A1/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010170715A (ja) | 2009-01-20 | 2010-08-05 | Toyota Motor Corp | 正極活物質材料 |
JP2011116580A (ja) | 2009-12-02 | 2011-06-16 | Sumitomo Metal Mining Co Ltd | ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 |
JP2014056661A (ja) | 2012-09-11 | 2014-03-27 | Toyota Motor Corp | 硫化物固体電解質 |
JP2015122298A (ja) * | 2013-11-22 | 2015-07-02 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質の製造方法、非水系電解質二次電池用正極活物質及びこれを用いた非水系電解質二次電池 |
JP2016076470A (ja) * | 2014-10-06 | 2016-05-12 | 日立金属株式会社 | リチウムイオン二次電池用正極活物質、それを用いたリチウムイオン二次電池用正極及びリチウムイオン二次電池 |
JP2019139854A (ja) * | 2018-02-06 | 2019-08-22 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法、非水系電解質二次電池用正極活物質の評価方法、および非水系電解質二次電池 |
JP2020087822A (ja) * | 2018-11-29 | 2020-06-04 | 住友金属鉱山株式会社 | リチウムニッケル含有複合酸化物とその製造方法、および、該リチウムニッケル含有複合酸化物を母材として用いたリチウムイオン二次電池用正極活物質とその製造方法 |
JP2020100541A (ja) * | 2018-12-20 | 2020-07-02 | 住友化学株式会社 | リチウム金属複合酸化物粉末、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池 |
JP2020129024A (ja) | 2019-02-07 | 2020-08-27 | コニカミノルタ株式会社 | 画像形成システム及び画像形成方法 |
JP2020167136A (ja) * | 2019-03-28 | 2020-10-08 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池 |
Non-Patent Citations (1)
Title |
---|
NARUMI OHTA ET AL.: "LiNbOs-coated LiCoO as cathode material for all solid-state lithium secondary batteries", ELECTROCHEMISTRY COMMUNICATIONS, vol. 9, 2007, pages 1486 - 1490, XP022118571, DOI: 10.1016/j.elecom.2007.02.008 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023181452A1 (ja) * | 2022-03-24 | 2023-09-28 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、リチウムイオン電池、全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池、リチウムイオン電池用正極活物質の製造方法及び全固体リチウムイオン電池用正極活物質の製造方法 |
WO2023182458A1 (ja) * | 2022-03-24 | 2023-09-28 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極、リチウムイオン電池、全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池、リチウムイオン電池用正極活物質の製造方法及び全固体リチウムイオン電池用正極活物質の製造方法 |
WO2023228958A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228957A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228956A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023228959A1 (ja) * | 2022-05-23 | 2023-11-30 | 住友金属鉱山株式会社 | 全固体リチウムイオン二次電池用正極活物質とその製造方法 |
WO2023238581A1 (ja) * | 2022-06-10 | 2023-12-14 | パナソニックホールディングス株式会社 | 被覆活物質、電極材料および電池 |
Also Published As
Publication number | Publication date |
---|---|
CN116157936A (zh) | 2023-05-23 |
JPWO2022025212A1 (ja) | 2022-02-03 |
EP4191703A1 (en) | 2023-06-07 |
US20230268500A1 (en) | 2023-08-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022025212A1 (ja) | 全固体リチウムイオン二次電池用正極活物質とその製造方法 | |
WO2018123951A1 (ja) | 非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 | |
WO2018043669A1 (ja) | 非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池 | |
US11594726B2 (en) | Positive electrode active material for lithium ion secondary battery, method for manufacturing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery | |
JP2020177860A (ja) | ニッケルマンガンコバルト含有複合水酸化物およびその製造方法、リチウムニッケルマンガンコバルト含有複合酸化物およびその製造方法、リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池 | |
WO2021251416A1 (ja) | リチウムイオン二次電池用正極活物質、その製造方法、およびリチウムイオン二次電池 | |
US20210305567A1 (en) | Positive electrode active material for lithium ion secondary battery, method of manufacturing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery | |
WO2021132512A1 (ja) | 全固体型リチウムイオン二次電池用正極活物質とその製造方法、および全固体型リチウムイオン二次電池 | |
JP7119783B2 (ja) | 遷移金属複合水酸化物の製造方法、遷移金属複合水酸化物、リチウムイオン二次電池用正極活物質の製造方法、リチウムイオン二次電池用正極活物質 | |
JP7274125B2 (ja) | 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池 | |
JP7177395B2 (ja) | 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池 | |
EP3951947A1 (en) | Positive-electrode active material for lithium-ion secondary cell, method for manufacturing positive-electrode active material, and lithium-ion secondary cell | |
US20220344656A1 (en) | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery | |
JP7272140B2 (ja) | リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池 | |
JP2021005548A (ja) | リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池 | |
WO2023228959A1 (ja) | 全固体リチウムイオン二次電池用正極活物質とその製造方法 | |
WO2023228958A1 (ja) | 全固体リチウムイオン二次電池用正極活物質とその製造方法 | |
JP2021005475A (ja) | リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池 | |
JP2020087858A (ja) | リチウムイオン二次電池用正極活物質の製造方法 | |
WO2023228957A1 (ja) | リチウムイオン二次電池用正極活物質とその製造方法 | |
JP2023172836A (ja) | 全固体リチウムイオン二次電池用正極活物質とその製造方法 | |
WO2020261962A1 (ja) | リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池 | |
JP2023172835A (ja) | 全固体リチウムイオン二次電池用正極活物質とその製造方法 | |
US20240021808A1 (en) | Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery | |
WO2023228956A1 (ja) | リチウムイオン二次電池用正極活物質とその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21851567 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022539579 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2021851567 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2021851567 Country of ref document: EP Effective date: 20230228 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |