JP6200959B2 - リチウム二次電池用正極活物質及びその製造方法 - Google Patents
リチウム二次電池用正極活物質及びその製造方法 Download PDFInfo
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- JP6200959B2 JP6200959B2 JP2015537653A JP2015537653A JP6200959B2 JP 6200959 B2 JP6200959 B2 JP 6200959B2 JP 2015537653 A JP2015537653 A JP 2015537653A JP 2015537653 A JP2015537653 A JP 2015537653A JP 6200959 B2 JP6200959 B2 JP 6200959B2
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- positive electrode
- active material
- lithium
- manganese
- electrode active
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- 239000007774 positive electrode material Substances 0.000 title claims description 68
- 229910052744 lithium Inorganic materials 0.000 title claims description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 41
- 229910052731 fluorine Inorganic materials 0.000 claims description 41
- 239000011737 fluorine Substances 0.000 claims description 41
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- -1 FeF 3 Inorganic materials 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims description 5
- 150000002642 lithium compounds Chemical class 0.000 claims description 5
- 150000002697 manganese compounds Chemical class 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 3
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- 229910016292 BiF 5 Inorganic materials 0.000 claims description 3
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 229910004573 CdF 2 Inorganic materials 0.000 claims description 3
- 229910016655 EuF 3 Inorganic materials 0.000 claims description 3
- 229910015475 FeF 2 Inorganic materials 0.000 claims description 3
- 229910005269 GaF 3 Inorganic materials 0.000 claims description 3
- 229910005690 GdF 3 Inorganic materials 0.000 claims description 3
- 229910004182 Hg 2 F 2 Inorganic materials 0.000 claims description 3
- 229910004379 HoF 3 Inorganic materials 0.000 claims description 3
- 229910017768 LaF 3 Inorganic materials 0.000 claims description 3
- 229910015275 MoF 6 Inorganic materials 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 229910019800 NbF 5 Inorganic materials 0.000 claims description 3
- 229910019595 ReF 6 Inorganic materials 0.000 claims description 3
- 229910018194 SF 6 Inorganic materials 0.000 claims description 3
- 229910018287 SbF 5 Inorganic materials 0.000 claims description 3
- 229910008449 SnF 2 Inorganic materials 0.000 claims description 3
- 229910004529 TaF 5 Inorganic materials 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 101100348958 Caenorhabditis elegans smf-3 gene Proteins 0.000 claims description 2
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 claims 1
- 239000006182 cathode active material Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 239000012528 membrane Substances 0.000 description 8
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 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 4
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- 229910018916 CoOOH Inorganic materials 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910016509 CuF 2 Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 239000004698 Polyethylene 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- KWIUXOZGRRITSH-UHFFFAOYSA-N 1,1-diethoxyethane;oxolane Chemical compound C1CCOC1.CCOC(C)OCC KWIUXOZGRRITSH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
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- 229910017008 AsF 6 Inorganic materials 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
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- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 229940097206 manganese citrate Drugs 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 150000004880 oxines Chemical class 0.000 description 1
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Description
また、本発明は、上述した正極活物質の製造方法を提供することを目的とする。
一般化学式(1)において、z>yであり、z>1−y−z≧0であり、x≧1である。
または、前記リチウムニッケル‐マンガン‐コバルト正極活物質の非制限的な例が下記の一般化学式(2)で表され得る。
一般化学式(2)において、z≧0.5である。
前記リチウムニッケル‐マンガン‐コバルト正極活物質は、最長直径20nm〜200μmの二次粒子を有し得る。
前記フッ素コーティングされた表面は、2nm〜20μmの厚さを有し得る。
一般化学式(1)において、Mn/Niの原子比率を表すz/yの値は1<z/y≦20であり得る。
(a)ニッケル化合物、マンガン化合物及びコバルト化合物を均一に混合する段階;
(b)リチウム化合物を添加し、焼成処理して層状のリチウムニッケル‐マンガン‐コバルト正極活物質を得る段階;及び
(c)層状のリチウムニッケル‐マンガン‐コバルト正極活物質の表面をフッ素コーティングして、フッ素コーティングされた表面がスピネル類似相を有するようにする段階。
前記フッ素コーティングは、熱処理固相方法、噴霧乾燥法または気相反応法によって行うことができる。
本発明の更に他の様態によれば、上述したリチウム二次電池を単位電池として含むことを特徴とする電池モジュールが提供される。
本発明の更に他の様態によれば、上述した電池モジュールを中大型デバイスの電源として含むことを特徴とする電池パックが提供される。
層状リチウムニッケル‐マンガン‐コバルト正極活物質は、ニッケル、マンガン、コバルトのうちMnが50重量%以上の組成を有する任意の正極活物質であり得、その非制限的な例が下記の一般化学式(1)で表され得るが、これに限定されることはない。
一般化学式(1)において、z>yであり、z>1−y−z≧0であり、x≧1である。
LixNiyMnzCo1-y-zMαO2 (2)
一般化学式(2)において、z>yであり、z>1−y−z≧0であり、x≧1であり、0≦α≦1であり、MはB、Li、Mg、Al、Ca、Sr、Cr、V、Ti、Fe、Co、Ni、Zr、Zn、Si、Y、Nb、Ga、Sn、Mo、W、及びこれらの組み合せからなる群より選択された1種以上の金属である。
また、Mn/Niの原子比率を表すz/yの値は1<z/y≦20であることが望ましい。
また、一般化学式(1)及び一般化学式(2)において、z≧0.5であることが望ましい。
前記リチウムニッケル‐マンガン‐コバルト正極活物質は、最長直径20nm〜200μmの粒子を有し得るが、これらに制限されることはない。
(a)ニッケル化合物、マンガン化合物及びコバルト化合物を均一に混合する段階;
(b)リチウム化合物を添加し、焼成処理して層状のリチウムニッケル‐マンガン‐コバルト正極活物質を得る段階;及び
(c)層状のリチウムニッケル‐マンガン‐コバルト正極活物質の表面をフッ素コーティングして、フッ素コーティングされた表面がスピネル類似相を有するようにする段階。
このようにして製造された本発明の正極活物質は、当業界で通常使用されるバインダー及び導電材と共に正極合剤を構成することができる。
上述した正極合剤スラリーは、正極集電体の上に塗布し、乾燥させてリチウム二次電池用正極を形成することができる。
正極集電体上の正極合剤スラリーの厚さは特に制限されないが、例えば10〜300μmであり得、活物質のローディング量は5〜50mg/cm2であり得る。
また、当技術分野で知られた通常の方法によって負極、分離膜、電解質を製造し、組立てて前記正極とともにリチウム二次電池を製作することができる。
層状のリチウムニッケル‐マンガン‐コバルト複合酸化物であるLiaNi0.4Mn0.6O2(1≦a<1.5)100gと、フッ素含有化合物であるPVdF 0.3gとを混合して、500℃で5〜10時間熱処理した。フッ素コーティングされたリチウムニッケル‐マンガン‐コバルト複合酸化物を得た。
実施例1で得た正極をリチウム二次電池の正極として使用した。
負極としては、一般に市販されるLi金属を使用した。
分離膜としては、ポリエチレンフィルムを使用して前記正極と前記負極との間に分離膜を介在させ、電解質としてEC/DMC/EMC=3/4/3混合溶媒に1molのLiPF6溶液を使用し、通常の製造方法によって電池を製造した。
層状のリチウムニッケル‐マンガン‐コバルト複合酸化物をフッ素コーティングせず使用したことを除き、実施例1と同じ方式で正極を製造した。
比較例1で得た正極を使用したことを除き、実施例2と同じ方法でリチウム二次電池を製造した。
実施例2及び比較例2で製造されたリチウム二次電池を4.65Vまで電流=0.1Cの条件で充電し、その容量を測定した。次いで、2.75Vまで電流=0.1Cで放電し、その容量を測定した。これらの結果を下記の表1に示した。
また、比較例2で最も優れた放電容量を示した電池セルと、実施例2の電池セルのレート容量比を図3に示した。
Claims (6)
- リチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法であって、
(a)ニッケル化合物、マンガン化合物及びコバルト化合物を均一に混合する段階と、
(b)リチウム化合物を添加し、焼成処理して、層状のリチウム‐ニッケル‐マンガン‐コバルト正極活物質を得る段階と、及び
(c)前記層状のリチウム‐ニッケル‐マンガン‐コバルト正極活物質に、フッ素含有化合物を付与し、還元雰囲気で焼成し、前記層状のリチウム‐ニッケル‐マンガン‐コバルト正極活物質の表面をフッ素コーティングして、前記フッ素コーティングされた前記層状のリチウム‐ニッケル‐マンガン‐コバルト正極活物質の表面がスピネル類似相を備えてなる段階とを含んでなり、
前記層状のリチウム‐ニッケル‐マンガン‐コバルト正極活物質が、下記の一般化学式(2)で表されることを特徴とする、リチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
Li x Ni y Mn z Co 1-y-z MαO 2 (化2)
〔前記一般化学式(2)において、
z>yであり、
z>1−y−z>0であり、
x≧1であり、
0≦α≦1であり、
MはB、Li、Mg、Al、Ca、Sr、Cr、V、Ti、Fe、Co、Ni、Zr、Zn、Si、Y、Nb、Ga、Sn、Mo、W、及びこれらの組み合せからなる群より選択された一種以上の金属である。〕 - 前記工程(c)が、300〜600℃の温度で、5〜10時間で行われることを特徴とする、請求項1に記載のリチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
- 前記リチウム‐ニッケル‐マンガン‐コバルト正極活物質が、最長直径20nm〜200μmの粒子を有することを特徴とする、請求項1又は2に記載のリチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
- 前記フッ素コーティングされた表面が、2nm〜20μmの厚さを有することを特徴とする、請求項1〜3の何れか一項に記載のリチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
- 前記フッ素コーティングに使用されるフッ素含有化合物が、ポリフッ化ビニリデン(PVdF)、AlF3、NH4F、CsF、KF、LiF、NaF、RbF、TiF、AgF、AgF2、BaF2、CaF2、CuF2、CdF2、FeF2、HgF2、Hg2F2、MnF2、MgF2、NiF2、PbF2、SnF2、SrF2、XeF2、ZnF2、AlF2、BF3、BiF3、CeF3、CrF3、DyF3、EuF3、GaF3、GdF3、FeF3、HoF3、InF3、LaF3、LuF3、MnF3、NdF3、VOF3、PrF3、SbF3、ScF3、SmF3、TbF3、TiF3、TmF3、YF3、YbF3、TIF3、CeF4、GeF4、HfF4、SiF4、SnF4、TiF4、VF4、ZrF4、NbF5、SbF5、TaF5、BiF5、MoF6、ReF6、SF6、WF6、フッ素含有ガス、及びこれらの混合物からなる群より選択された化合物からなることを特徴とする、請求項1〜4の何れか一項に記載のリチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
- 前記フッ素コーティングに使用されるフッ素含有化合物が、ポリフッ化ビニリデン(PVdF)であることを特徴とする、請求項1〜4の何れか一項に記載のリチウム二次電池用リチウム‐ニッケル‐マンガン‐コバルト正極活物質の製造方法。
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JP6172529B2 (ja) * | 2014-07-22 | 2017-08-02 | トヨタ自動車株式会社 | リチウムイオン二次電池用正極活物質およびその利用 |
US10109858B1 (en) * | 2015-05-08 | 2018-10-23 | Tronox Llc | Method for preparing electrolytic manganese dioxide |
KR101770820B1 (ko) | 2015-07-09 | 2017-08-23 | 이환 | 양극 활물질용 리튬망간산화물의 제조방법 |
CN106356507B (zh) * | 2015-07-13 | 2021-05-04 | 三星电子株式会社 | 用于锂电池的复合正极活性材料、其制备方法、用于锂电池的正极和锂电池 |
KR102547064B1 (ko) * | 2016-03-18 | 2023-06-23 | 삼성에스디아이 주식회사 | 유기전해액 및 상기 전해액을 채용한 리튬 전지 |
CN109476507B (zh) * | 2016-04-29 | 2021-11-09 | 汉阳大学校产学协力团 | 正极活性物质、其制备方法及包含其的锂二次电池 |
KR20180018884A (ko) * | 2016-08-09 | 2018-02-22 | 인천대학교 산학협력단 | 수계 리튬이차전지용 표면 처리된 양극 활물질 |
US20180145317A1 (en) * | 2016-11-18 | 2018-05-24 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
CN106935799B (zh) * | 2017-03-17 | 2018-10-12 | 江苏润寅石墨烯科技有限公司 | 一种稳定的镍钴锰酸锂三元锂电池正极片及制备方法 |
KR102266508B1 (ko) * | 2017-09-26 | 2021-06-16 | 주식회사 엘지에너지솔루션 | 전지 급속 충전 시스템 |
KR102164006B1 (ko) | 2017-11-16 | 2020-10-12 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이를 포함하는 리튬 이차 전지 및 전지모듈 |
CN107959015B (zh) * | 2017-11-23 | 2018-11-16 | 江苏贝肯盛创新能源科技有限公司 | 一种改性锂电池正极材料、制备方法及包含其的锂电池 |
CN108511710B (zh) * | 2018-03-22 | 2020-09-11 | 中南大学 | 富锂锰基锂离子电池正极材料及其制备方法 |
KR20190130932A (ko) | 2018-05-15 | 2019-11-25 | 삼성에스디아이 주식회사 | 리튬이차전지용 양극활물질 및 이를 포함하는 양극을 포함한 리튬이차전지 |
DE102018114009A1 (de) * | 2018-06-12 | 2019-12-12 | Volkswagen Aktiengesellschaft | Aktivmaterialkörper für einen Akkumulator |
JP7186866B2 (ja) * | 2018-09-28 | 2022-12-09 | エルジー・ケム・リミテッド | 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 |
US11495796B2 (en) | 2018-11-14 | 2022-11-08 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
US11757092B2 (en) | 2018-11-15 | 2023-09-12 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
JP2020087810A (ja) * | 2018-11-29 | 2020-06-04 | セイコーエプソン株式会社 | 活物質、活物質の製造方法、電極複合体、二次電池および電子機器 |
KR102363371B1 (ko) * | 2019-02-01 | 2022-02-14 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100441520B1 (ko) | 2002-05-28 | 2004-07-23 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질 및 그 제조방법 |
KR100565990B1 (ko) | 2003-11-24 | 2006-03-30 | 전자부품연구원 | 리튬 2차전지용 양극 활물질, 그 제조 방법 및 그를포함하는 리튬 2차전지 |
JP2006012426A (ja) * | 2004-06-22 | 2006-01-12 | Nichia Chem Ind Ltd | 非水電解質二次電池用正極活物質および非水電解質二次電池 |
JP4582579B2 (ja) * | 2004-12-07 | 2010-11-17 | Agcセイミケミカル株式会社 | リチウム二次電池用正極材料 |
KR100822013B1 (ko) | 2005-04-15 | 2008-04-14 | 주식회사 에너세라믹 | 불소화합물코팅 리튬이차전지 양극 활물질 및 그 제조방법 |
JP5223166B2 (ja) * | 2006-02-07 | 2013-06-26 | 日産自動車株式会社 | 電池活物質および二次電池 |
US8142932B2 (en) * | 2006-12-05 | 2012-03-27 | Sk Innovation Co., Ltd. | Core-shell spinel cathode active materials for lithium secondary batteries, lithium secondary batteries using the same and method for preparing thereof |
JP4258676B2 (ja) * | 2007-03-05 | 2009-04-30 | 戸田工業株式会社 | 非水電解質二次電池用Li−Ni複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池 |
US8389160B2 (en) * | 2008-10-07 | 2013-03-05 | Envia Systems, Inc. | Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials |
JP5111421B2 (ja) * | 2009-03-27 | 2013-01-09 | 株式会社日立製作所 | リチウム二次電池用正極材料,リチウム二次電池及びそれを用いた二次電池モジュール |
JP5791877B2 (ja) * | 2009-09-30 | 2015-10-07 | 三洋電機株式会社 | 正極活物質、この正極活物質の製造方法、及び、正極活物質を用いた非水電解質二次電池 |
US8852452B2 (en) * | 2009-11-05 | 2014-10-07 | Umicore | Core-shell lithium transition metal oxides |
JP5645092B2 (ja) | 2009-11-05 | 2014-12-24 | ユミコア | 二重シェルコアリチウムニッケルマンガンコバルト酸化物 |
JP2011171150A (ja) * | 2010-02-19 | 2011-09-01 | Sony Corp | 正極活物質、正極および非水電解質二次電池 |
US8741484B2 (en) | 2010-04-02 | 2014-06-03 | Envia Systems, Inc. | Doped positive electrode active materials and lithium ion secondary battery constructed therefrom |
JP5621600B2 (ja) * | 2011-01-11 | 2014-11-12 | 旭硝子株式会社 | リチウムイオン二次電池用の正極活物質およびその製造方法 |
JP6086501B2 (ja) * | 2011-04-18 | 2017-03-01 | エルジー ケム. エルティーディ. | 正極活物質、及びそれを含むリチウム二次電池 |
CN104011912B (zh) * | 2011-05-23 | 2016-05-04 | 株式会社Lg化学 | 具有增强的能量密度特性的高能量密度锂二次电池 |
JPWO2012176903A1 (ja) * | 2011-06-24 | 2015-02-23 | 旭硝子株式会社 | リチウムイオン二次電池用正極活物質の製造方法 |
KR20130033154A (ko) * | 2011-09-26 | 2013-04-03 | 전자부품연구원 | 리튬 이차전지용 양극 활물질, 그의 제조방법 및 그를 포함하는 리튬이차전지 |
JP5831769B2 (ja) * | 2011-11-16 | 2015-12-09 | トヨタ自動車株式会社 | リチウムイオン二次電池及びその製造方法 |
KR101400593B1 (ko) | 2012-12-06 | 2014-05-27 | 삼성정밀화학 주식회사 | 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 |
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US20150287984A1 (en) | 2015-10-08 |
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CN104781964A (zh) | 2015-07-15 |
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