JP2021520035A - リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 - Google Patents
リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 Download PDFInfo
- Publication number
- JP2021520035A JP2021520035A JP2020556267A JP2020556267A JP2021520035A JP 2021520035 A JP2021520035 A JP 2021520035A JP 2020556267 A JP2020556267 A JP 2020556267A JP 2020556267 A JP2020556267 A JP 2020556267A JP 2021520035 A JP2021520035 A JP 2021520035A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- electrode active
- transition metal
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 213
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 78
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 171
- 239000002245 particle Substances 0.000 claims abstract description 94
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 90
- 239000010941 cobalt Substances 0.000 claims abstract description 90
- 239000011572 manganese Substances 0.000 claims abstract description 90
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 80
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 73
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000011164 primary particle Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 238000005259 measurement Methods 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 239000011163 secondary particle Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 104
- 150000003624 transition metals Chemical class 0.000 claims description 94
- 239000000243 solution Substances 0.000 claims description 81
- 239000002994 raw material Substances 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 49
- 230000007423 decrease Effects 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 230000004931 aggregating effect Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 52
- -1 Lithium transition metal Chemical class 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 20
- 239000007773 negative electrode material Substances 0.000 description 20
- 241000080590 Niso Species 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004020 conductor Substances 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 7
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical group 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910000925 Cd alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000001687 destabilization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920005608 sulfonated EPDM Polymers 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000006234 thermal black Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010090 LiAlO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910016811 Ni0.65CO0.20Mn0.15 Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- GWWNCLHJCFNTJA-UHFFFAOYSA-N nicandrenone-2 Natural products C12OC2C2(O)CC=CC(=O)C2(C)C(CCC23C)C1C3CCC2(O)C(C)C1OC(O)C2(C)OC2(C)C1 GWWNCLHJCFNTJA-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/36—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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
Abstract
Description
本出願は、2018年5月11日付韓国特許出願第2018−0054292号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
[化学式1]
Li1+aNixCoyMnzM1 WO2
前記化学式1において、0≦a≦0.3、0.65≦x<1、0<y≦0.35、0<z≦0.35、0≦w≦0.02、y<zであり、M1は、Al、Zr、Mg、Zn、Y、Fe及びTiからなる群から選択された少なくとも一つである。
従来、リチウム二次電池の正極活物質としては、作用電圧が高く、容量特性に優れたリチウムコバルト系酸化物が用いられたが、前記リチウムコバルト系酸化物は、脱リチウムによる結晶構造の不安定化のため熱的特性が劣化し、高価であるため中大型デバイスの動力源として大量使用するには限界があった。前記リチウムコバルト系酸化物を代替するためにリチウムニッケルコバルトマンガン系酸化物を用いたが、前記リチウムニッケルコバルトマンガン系酸化物の場合、製造コストを低減するためにコバルトの含量を減少するに伴い、放電容量及び出力特性が減少されるという問題点があった。
[化学式1]
Li1+aNixCoyMnzM1 WO2
前記化学式1において、
0≦a≦0.3、0.65≦x<1、0<y≦0.35、0<z≦0.35、0≦w≦0.02、y<zであり、
M1は、Al、Zr、Mg、Zn、Y、Fe及びTiからなる群から選択された少なくとも一つである。
次に、本発明に係る正極活物質の製造方法に対して説明する。
具体的に、ニッケル原料物質としては、Ni(OH)2、NiO、NiOOH、NiCO3・2Ni(OH)2・4H2O、NiC2O2・2H2O、Ni(NO3)2・6H2O、NiSO4、NiSO4・6H2O、脂肪酸ニッケル塩またはニッケルハロゲン化物などを挙げることができ、これらのうち1種以上の混合物が用いられてよい。
次に、本発明に係る正極活物質を含む、リチウム二次電池用正極を提供する。
また、本発明は、前記正極を含む電気化学素子を製造することができる。前記電気化学素子は、具体的に電池、キャパシタなどであってよく、より具体的にはリチウム二次電池であってよい。
(正極活物質の製造)
NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備した。
前記で製造された正極活物質、デンカブラック導電材、及びポリビニリデンフルオライド(PVDF)バインダを95:2.5:2.5の重量比で混合し、これをN‐メチルピロリドン(NMP)溶媒中で混合して正極スラリーを製造した。前記で製造された正極スラリーをアルミニウムホイルに塗布した後、ロールプレスを行い、120℃で12時間乾燥して正極を製造した。
負極活物質として天然黒鉛、カーボンブラック導電材、及びスチレン‐ブタジエンゴム(SBR)バインダを96:2:2の重量比で混合して負極スラリーを製造した。これを銅ホイル上に塗布し、110℃で2時間真空乾燥して負極を製造した後、ロールプレスを行った。
前記で製造した正極、負極と、厚さ20μmのポリエチレン分離膜(F20BHE、東燃社)を用いて通常の方法でコインセル形態の電池を製造した後、エチレンカーボネート:ジメチルカーボネートを1:1(体積%)で混合した溶媒に、1MのLiPF6を溶解させた電解液を注入し、コインセル形態のリチウム二次電池を製造した。
正極活物質の製造時、NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備し、さらに、NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が55:20.5:24.5となるようにする量で、水中で混合して2.3M濃度の第2遷移金属含有溶液を準備した。前記第1遷移金属含有溶液及び第2遷移金属含有溶液を用いて、平均組成がNi0.65Co0.15Mn0.2(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記実施例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
正極活物質の製造時、NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備し、さらに、NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が55:13.5:31.5となるようにする量で、水中で混合して2.3M濃度の第2遷移金属含有溶液を準備した。前記第1遷移金属含有溶液及び第2遷移金属含有溶液を用いて、Ni0.65Co0.10Mn0.25(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記実施例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
正極活物質の製造時、NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備し、さらに、NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が55:17:28となるようにする量で、水中で混合して2.3M濃度の第2遷移金属含有溶液を準備した。前記第1遷移金属含有溶液及び第2遷移金属含有溶液を用いて、Ni0.65Co0.125Mn0.225(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記実施例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が70:10:20となるようにする量で、水中で混合して2.3M濃度の遷移金属含有溶液を準備した。
反応全体に亘って反応器内のpHをpH11.2に維持することを除き、前記実施例1と同様の方法を用いて正極活物質及びこれを含む正極及び二次電池を製造した。
NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が65:15:20となるようにする量で、水中で混合して2.3M濃度の遷移金属含有溶液を準備し、これを用いて、Ni0.65Co0.15Mn0.20(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記比較例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が65:12.5:22.5となるようにする量で、水中で混合して2.3M濃度の遷移金属含有溶液を準備し、これを用いて、Ni0.65Co0.125Mn0.225(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記比較例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が65:20:15となるようにする量で、水中で混合して2.3M濃度の遷移金属含有溶液を準備し、これを用いて、Ni0.65Co0.20Mn0.15(OH)2である正極活物質前駆体を製造し、これを用いることを除き、前記比較例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
NiSO4、CoSO4、及びMnSO4をニッケル:コバルト:マンガンのモル比が65:17.5:17.5となるようにする量で、水中で混合して2.3M濃度の遷移金属含有溶液を準備し、これを用いて、Ni0.65Co0.175Mn0.175(OH)4である正極活物質前駆体を製造し、これを用いることを除き、前記比較例1と同様の方法を用いて正極活物質及びこれを含む正極及びリチウム二次電池を製造した。
NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備した。
NiSO4及びMnSO4をニッケル:マンガンのモル比が95:5となるようにする量で、水中で混合して2.3M濃度の第1遷移金属含有溶液を準備した。
前記実施例1及び比較例1及び2で製造した正極活物質粒子を切断して透過電子顕微鏡(TEM)を用いて正極活物質の断面を撮影し、前記正極活物質の表面の結晶構造を制限視野回折パターン(selected area diffraction pattern,SADP)を介して確認した。
前記実施例1〜4及び比較例1〜6で製造した二次電池に対して充放電効率評価を行い、その結果を下記表1に示した。
前記実施例1〜2及び比較例1〜6で製造したリチウム二次電池の低温(−10℃)出力特性を確認した。具体的に、前記実施例1〜2及び比較例1〜6で製造したリチウム二次電池を常温(25℃)で0.33C定電流で充電させた後、22.5分間0.4C定電流で放電させ、1,350秒間の電圧降下を測定し、これを下記表2に示した。
前記実施例1〜4及び比較例1〜8で製造した正極を含む二次電池の寿命特性及び抵抗特性を測定した。具体的に、前記実施例1〜4及び比較例1〜8で製造した二次電池を、それぞれ45℃で1Cの定電流で4.25Vまで3Cカットオフ(cut off)で充電した。その後、1C定電流で3.0Vになるまで放電をした。前記充電及び放電挙動を1サイクルとし、このようなサイクルを300回繰り返して行った後、前記実施例1〜4及び比較例1〜8による二次電池のサイクルによる容量維持率及び抵抗増加率を測定した。前記寿命特性の場合、300サイクル目での容量を初期容量で割った後、100を掛けてその値を計算しており、前記抵抗特性の場合、300サイクル目での抵抗を初期抵抗で割った後、100を掛けてその値を計算した後、これを下記表3及び図5に示した。
Claims (12)
- 平均組成が下記化学式1で表されるリチウム遷移金属酸化物を含み、前記リチウム遷移金属酸化物内のコバルト含量がマンガン含量より少ない正極活物質であって、
前記リチウム遷移金属酸化物は、ニッケル、コバルト及びマンガンのうち少なくともいずれか一つが粒子の中心から表面まで漸進的に変化する濃度勾配を有し、
前記正極活物質は、1次粒子が凝集されてなる2次粒子の形態であり、
前記正極活物質の表面の少なくとも8箇所の地点でTEM分析を介して測定したc軸方向と測定地点の粒子成長方向がなす角度が85゜から95゜を満たす比率が60%以上であり、
[化学式1]
Li1+aNixCoyMnzM1 WO2
前記化学式1において、
0≦a≦0.3、0.65≦x<1、0<y≦0.35、0<z≦0.35、0≦w≦0.02、y<zであり、
M1は、Al、Zr、Mg、Zn、Y、Fe及びTiからなる群から選択された少なくとも一つである、正極活物質。 - 前記リチウム遷移金属酸化物のコバルト:マンガンのモル比が1:1超過1:10以下である、請求項1に記載の正極活物質。
- 前記正極活物質は、表面部に前記正極活物質の中心から表面方向に成長した柱状構造の1次粒子を含む、請求項1または2に記載の正極活物質。
- 前記化学式1で表されるリチウム遷移金属酸化物は、リチウムを除いた遷移金属の総モル数に対してコバルトを15モル%以下で含む、請求項1から3のいずれか一項に記載の正極活物質。
- 前記化学式1で表されるリチウム遷移金属酸化物は、リチウムを除いた遷移金属の総モル数に対してマンガンを20モル%以上35モル%未満で含む、請求項1から4のいずれか一項に記載の正極活物質。
- ニッケル原料物質を含む第1遷移金属含有溶液と、
前記第1遷移金属含有溶液と異なる遷移金属濃度を有し、且つ、ニッケル原料物質、コバルト原料物質及びマンガン原料物質を含む第2遷移金属含有溶液とを準備する段階、
前記第1遷移金属含有溶液及び第2遷移金属含有溶液の混合比率を漸進的に変化させながら、前記第1遷移金属含有溶液と第2遷移金属含有溶液とを混合して正極活物質前駆体を製造する段階、及び
前記正極活物質前駆体及びリチウム含有原料物質を混合して焼成し、正極活物質を合成する段階、を含み、
前記正極活物質前駆体を製造する段階は、混合溶液内のニッケル含量が減少するに伴い、pHが漸進的に低くなるように調節される、正極活物質の製造方法。 - 前記第1遷移金属含有溶液のニッケル:コバルト:マンガンのモル比が(80〜100):(0〜10):(0〜20)である、請求項6に記載の正極活物質の製造方法。
- 前記第2遷移金属含有溶液のニッケル:コバルト:マンガンのモル比が(50〜80):(10〜30):(10〜35)である、請求項6に記載の正極活物質の製造方法。
- 前記pHは、pH13からpH9の範囲で漸進的に減少する、請求項6から8のいずれか一項に記載の正極活物質の製造方法。
- 前記正極活物質前駆体及び前記リチウム含有原料物質の混合時、ドーピング元素M1原料物質をさらに加え、M1は、Al、Zr、Mg、Zn、Y、Fe及びTiからなる群から選択された少なくとも一つである、請求項6から9のいずれか一項に記載の正極活物質の製造方法。
- 請求項1から5のいずれか一項に記載の正極活物質を含む、リチウム二次電池用正極。
- 請求項11に記載の正極を含む、リチウム二次電池。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023101075A JP2023134475A (ja) | 2018-05-11 | 2023-06-20 | リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2018-0054292 | 2018-05-11 | ||
KR1020180054292A KR102302038B1 (ko) | 2018-05-11 | 2018-05-11 | 리튬 이차전지용 양극 활물질, 이의 제조방법, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지 |
PCT/KR2019/005631 WO2019216694A1 (ko) | 2018-05-11 | 2019-05-10 | 리튬 이차전지용 양극 활물질, 이의 제조방법, 이를 포함하는 리튬 이차전지용 양극 및 리튬 이차전지 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2023101075A Division JP2023134475A (ja) | 2018-05-11 | 2023-06-20 | リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2021520035A true JP2021520035A (ja) | 2021-08-12 |
Family
ID=68468160
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020556267A Pending JP2021520035A (ja) | 2018-05-11 | 2019-05-10 | リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 |
JP2023101075A Pending JP2023134475A (ja) | 2018-05-11 | 2023-06-20 | リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2023101075A Pending JP2023134475A (ja) | 2018-05-11 | 2023-06-20 | リチウム二次電池用正極活物質、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 |
Country Status (5)
Country | Link |
---|---|
US (2) | US11799071B2 (ja) |
JP (2) | JP2021520035A (ja) |
KR (1) | KR102302038B1 (ja) |
CN (1) | CN112005411A (ja) |
WO (1) | WO2019216694A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020087814A (ja) * | 2018-11-29 | 2020-06-04 | 本田技研工業株式会社 | 正極活物質粒子 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109148894A (zh) * | 2018-09-05 | 2019-01-04 | 天津瑞晟晖能科技有限公司 | 锂离子电池正极、全固态锂离子电池及其制备方法与用电器件 |
CN111564625A (zh) * | 2020-04-07 | 2020-08-21 | 江门市科恒实业股份有限公司 | 一种单晶三元正极材料及其制备方法 |
US20230290942A1 (en) * | 2020-09-24 | 2023-09-14 | Lg Chem, Ltd. | Solid Phase Synthesis Method of Positive Electrode Active Material of Nickel-Rich Lithium Composite Transition Metal Oxide in a Form of a Single Particle, Positive Electrode Active Material of Nickel-Rich Lithium Composite Transition Metal Oxide in a Form of a Single Particle Formed Therefrom, Positive Electrode and Lithium Secondary Battery Containing the Same |
KR102624905B1 (ko) * | 2020-11-25 | 2024-01-12 | (주)포스코퓨처엠 | 배향성 구조를 갖는 리튬전지용 양극활물질 및 이의 제조방법 |
CN112599761B (zh) * | 2020-12-11 | 2022-03-18 | 宁德新能源科技有限公司 | 电化学装置和电子装置 |
CN116799286A (zh) * | 2021-02-20 | 2023-09-22 | 宁德新能源科技有限公司 | 电化学装置及包括其的电子装置 |
DE102021204702A1 (de) | 2021-05-10 | 2022-11-10 | Volkswagen Aktiengesellschaft | Sekundärpartikel für eine Kathode einer sekundären Lithium-Batteriezelle sowie Verfahren zur Herstellung eines Solchen |
CN114122385B (zh) * | 2022-01-26 | 2022-04-26 | 瑞浦能源有限公司 | 一种锂离子电池用低钴三元正极材料及其制备方法、锂离子电池正极极片和锂离子电池 |
CN115196683B (zh) * | 2022-07-19 | 2023-10-20 | 欣旺达动力科技股份有限公司 | 一种正极材料、二次电池及用电设备 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014061654A1 (ja) * | 2012-10-17 | 2014-04-24 | 戸田工業株式会社 | Li-Ni複合酸化物粒子粉末並びに非水電解質二次電池 |
WO2017095133A1 (ko) * | 2015-11-30 | 2017-06-08 | 주식회사 엘지화학 | 이차전지용 양극활물질 및 이를 포함하는 이차전지 |
KR101849719B1 (ko) * | 2012-06-08 | 2018-04-19 | 한양대학교 산학협력단 | 리튬 이차 전지용 양극활물질 전구체, 이를 이용하여 제조된 양극활물질 및 이를 포함하는 리튬 이차 전지 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2940761B1 (en) | 2012-12-26 | 2019-12-18 | IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) | Cathode active material for lithium secondary batteries |
KR102124052B1 (ko) | 2013-10-18 | 2020-06-17 | 삼성전자주식회사 | 양극 활물질, 그 제조방법 및 이를 포함한 양극을 구비한 리튬 전지 |
KR101610364B1 (ko) | 2014-09-16 | 2016-04-08 | 주식회사 포스코 | 리튬 이차 전지용 양극 활물질, 그 제조방법 및 이를 사용한 리튬 이차 전지 |
JP6564064B2 (ja) | 2015-04-30 | 2019-08-21 | エルジー・ケム・リミテッド | 二次電池用正極活物質、この製造方法及びこれを含む二次電池 |
KR101913906B1 (ko) | 2015-06-17 | 2018-10-31 | 주식회사 엘지화학 | 이차전지용 양극활물질, 이의 제조방법 및 이를 포함하는 이차전지 |
KR101913897B1 (ko) | 2015-09-30 | 2018-12-28 | 주식회사 엘지화학 | 이차전지용 양극활물질 및 이를 포함하는 이차전지 |
KR101927295B1 (ko) | 2015-11-30 | 2018-12-10 | 주식회사 엘지화학 | 이차전지용 양극활물질 및 이를 포함하는 이차전지 |
KR102521323B1 (ko) | 2015-12-09 | 2023-04-13 | 에스케이온 주식회사 | 리튬이차전지 |
-
2018
- 2018-05-11 KR KR1020180054292A patent/KR102302038B1/ko active IP Right Grant
-
2019
- 2019-05-10 WO PCT/KR2019/005631 patent/WO2019216694A1/ko active Application Filing
- 2019-05-10 JP JP2020556267A patent/JP2021520035A/ja active Pending
- 2019-05-10 CN CN201980027475.0A patent/CN112005411A/zh active Pending
- 2019-05-10 US US17/050,553 patent/US11799071B2/en active Active
-
2023
- 2023-06-20 JP JP2023101075A patent/JP2023134475A/ja active Pending
- 2023-09-08 US US18/243,974 patent/US20230420649A1/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101849719B1 (ko) * | 2012-06-08 | 2018-04-19 | 한양대학교 산학협력단 | 리튬 이차 전지용 양극활물질 전구체, 이를 이용하여 제조된 양극활물질 및 이를 포함하는 리튬 이차 전지 |
WO2014061654A1 (ja) * | 2012-10-17 | 2014-04-24 | 戸田工業株式会社 | Li-Ni複合酸化物粒子粉末並びに非水電解質二次電池 |
WO2017095133A1 (ko) * | 2015-11-30 | 2017-06-08 | 주식회사 엘지화학 | 이차전지용 양극활물질 및 이를 포함하는 이차전지 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020087814A (ja) * | 2018-11-29 | 2020-06-04 | 本田技研工業株式会社 | 正極活物質粒子 |
Also Published As
Publication number | Publication date |
---|---|
KR20190129518A (ko) | 2019-11-20 |
KR102302038B1 (ko) | 2021-09-15 |
WO2019216694A1 (ko) | 2019-11-14 |
US20230420649A1 (en) | 2023-12-28 |
US11799071B2 (en) | 2023-10-24 |
JP2023134475A (ja) | 2023-09-27 |
CN112005411A (zh) | 2020-11-27 |
US20210234155A1 (en) | 2021-07-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7139008B2 (ja) | 二次電池用正極活物質、その製造方法及びこれを含むリチウム二次電池 | |
JP7034409B2 (ja) | リチウム二次電池用正極活物質、その製造方法、それを含むリチウム二次電池用正極及びリチウム二次電池 | |
JP7048853B2 (ja) | リチウム二次電池用正極材、この製造方法、これを含むリチウム二次電池用正極及びリチウム二次電池 | |
US11799071B2 (en) | Positive electrode active material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which include the positive electrode active material | |
JP2022507671A (ja) | リチウム二次電池用正極活物質及びこの製造方法 | |
JP7009013B2 (ja) | リチウム二次電池用正極活物質前駆体の製造方法 | |
JP7254407B2 (ja) | 正極活物質前駆体の製造方法および正極活物質前駆体 | |
KR102490392B1 (ko) | 리튬 이차전지용 양극 활물질 전구체의 제조 방법, 양극 활물질 전구체, 이를 이용하여 제조된 양극 활물질, 양극 및 리튬 이차전지 | |
JP2022501789A (ja) | 二次電池用正極活物質、その製造方法及びそれを含むリチウム二次電池 | |
JP7451728B2 (ja) | 二次電池用正極活物質前駆体、正極活物質およびこれを含むリチウム二次電池 | |
JP2020528643A (ja) | リチウム二次電池用正極材、この製造方法、これを含むリチウム二次電池用正極、及びリチウム二次電池 | |
KR20210097057A (ko) | 이차전지용 양극 활물질 전구체, 양극 활물질 및 이를 포함하는 리튬 이차전지 | |
JP7460258B2 (ja) | 正極活物質前駆体及びその製造方法 | |
JP7225415B2 (ja) | 二次電池用正極活物質の製造方法 | |
JP2022516955A (ja) | リチウム二次電池用正極活物質の製造方法、および前記製造方法により製造された正極活物質 | |
KR20210017554A (ko) | 이차전지용 양극 활물질의 제조방법 | |
KR102369333B1 (ko) | 리튬 이차전지용 양극 활물질 전구체의 제조 방법 및 상기 제조 방법에 의해 제조된 양극 활물질 전구체 | |
JP2023550404A (ja) | 正極活物質前駆体、その製造方法および正極活物質 | |
JP2024501306A (ja) | 正極活物質、これを含む正極および二次電池 | |
KR102304738B1 (ko) | 리튬 이차전지용 양극 활물질 전구체의 제조 방법 | |
EP4167323A1 (en) | Cathode active material precursor and manufacturing method therefor | |
JP2023539086A (ja) | 正極活物質前駆体、その製造方法およびこれを用いた正極活物質の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201013 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211115 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220214 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220711 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221011 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230220 |