JP2020083677A - Nickel-manganese-based composite oxide and method for producing the same - Google Patents
Nickel-manganese-based composite oxide and method for producing the same Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000013078 crystal Substances 0.000 claims abstract description 74
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 65
- 150000003624 transition metals Chemical class 0.000 claims abstract description 65
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 63
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 66
- 235000002639 sodium chloride Nutrition 0.000 claims description 58
- 239000011780 sodium chloride Substances 0.000 claims description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims description 25
- 159000000002 lithium salts Chemical class 0.000 claims description 25
- 238000002441 X-ray diffraction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 20
- 150000002816 nickel compounds Chemical class 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 150000002697 manganese compounds Chemical class 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000009279 wet oxidation reaction Methods 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052744 lithium Inorganic materials 0.000 abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011435 rock Substances 0.000 abstract 2
- 229910003289 NiMn Inorganic materials 0.000 abstract 1
- 238000011156 evaluation Methods 0.000 description 47
- 239000000843 powder Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- DHRPEFZPRLLJIX-UHFFFAOYSA-M C(C)(=O)[O-].C(C)(=O)[Mn+] Chemical compound C(C)(=O)[O-].C(C)(=O)[Mn+] DHRPEFZPRLLJIX-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910007287 Li2S—SiS2—Li2PO4 Inorganic materials 0.000 description 1
- 229910014411 LiNi1/2Mn1/2O2 Inorganic materials 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
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910008065 Si-SiO Inorganic materials 0.000 description 1
- 229910006405 Si—SiO Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- AHSBSUVHXDIAEY-UHFFFAOYSA-K manganese(iii) acetate Chemical compound [Mn+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AHSBSUVHXDIAEY-UHFFFAOYSA-K 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide 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
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- 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
本発明は、ニッケル含有リチウムマンガン複合酸化物及びその製造方法に関する。 The present invention relates to a nickel-containing lithium manganese composite oxide and a method for producing the same.
我が国において開発されたリチウムイオン二次電池は、ノートパソコンや携帯電話などの小型民生機器用電源のみならず、電気自動車や発電所併設の電力負荷平準化機器として実用化されつつあり、その大型化への対応が急務となってきている。リチウムイオン構成部材の中で正極活物質は最も高コストであり、容量も決定づける重要なものである。正極活物質として最初に実用化されたのはコバルト酸リチウムであったが、コバルト資源が希少かつ政情不安な国々に偏在しているために、大型電池向けには避けられる傾向がある。代替正極材料としてニッケル酸リチウム、マンガン酸リチウムが提案されているが、前者は充電時の化学的安定性が低く電池の安全性確保が困難なこと、後者はリチウム含有量が前者の半分で充放電容量が低いことが問題とされ、それらの問題を解決する代替材料開発が期待されている。 The lithium-ion secondary battery developed in Japan is being put to practical use not only as a power source for small consumer devices such as laptop computers and mobile phones, but also as a power load leveling device for electric vehicles and power stations. There is an urgent need to respond to. Among the lithium ion constituent members, the positive electrode active material has the highest cost and is important in determining the capacity. Although lithium cobalt oxide was first put into practical use as a positive electrode active material, it tends to be avoided for large batteries because cobalt resources are ubiquitous in countries that are scarce and politically unstable. Lithium nickel oxide and lithium manganate have been proposed as alternative cathode materials, but the former has low chemical stability during charging and it is difficult to secure battery safety.The latter has a lithium content of half that of the former. The problem is that the discharge capacity is low, and the development of alternative materials to solve these problems is expected.
このような代替材料候補としてLiNi1/2Mn1/2O2に代表される、4V級のニッケルマンガン複合酸化物が2001年に提案されている（例えば、非特許文献１参照）。この材料はNiO-Li2MnO3固溶体に属し、0.5NiO-0.5Li2MnO3組成に相当する。この材料は非特許文献１よりコバルト酸リチウムより安全性が高く、且つ4.6Vまでの高充電電位でも安定したサイクル特性を有すること、格子定数がa= 2.89Å、c= 14.30Åの六方晶層状岩塩型結晶相1相のみからなることが知られている。この正極活物質の問題点は、遷移金属イオンが多くリチウム層内に入ることであり、その低減のためにコバルト置換が検討されニッケルマンガンコバルト複合酸化物を用いたNMC正極と言われる今日の実用正極材料が開発された経緯がある。このNMC正極に関して非常に多くの特許出願がなされている（例えば、特許文献１参照）。NMC正極には結局コバルトが用いられていることから、充電時における化学安定性の低さに課題があり、かかる化学安定性の低さは、電池の安全性及び高上限電位設定時のサイクル特性に問題をきたすことがあり、コバルトを含まない正極材料の必要性は依然として薄れていない。 As such an alternative material candidate, a 4V-class nickel manganese composite oxide represented by LiNi 1/2 Mn 1/2 O 2 has been proposed in 2001 (for example, see Non-Patent Document 1). This material belongs to the NiO-Li 2 MnO 3 solid solution and corresponds to the 0.5NiO-0.5Li 2 MnO 3 composition. This material has higher safety than lithium cobalt oxide according to Non-Patent Document 1, and has stable cycle characteristics even at a high charge potential up to 4.6 V, and a hexagonal layered structure with lattice constants of a = 2.89Å, c = 14.30Å. It is known that the rock salt type crystal phase consists of only one phase. The problem with this positive electrode active material is that a large amount of transition metal ions enter the lithium layer, and cobalt substitution has been studied to reduce it, and it is said that the NMC positive electrode using nickel manganese cobalt composite oxide is practically used today. There is a history of development of positive electrode materials. Numerous patent applications have been made for this NMC positive electrode (see, for example, Patent Document 1). Since cobalt is used for the NMC positive electrode after all, there is a problem in low chemical stability during charging, and such low chemical stability is due to battery safety and cycle characteristics when setting a high upper limit potential. The need for cobalt-free cathode materials is still diminishing.
ところで、上記したニッケルマンガン複合酸化物において、リチウム過剰とした場合には均一且つ単独の層状岩塩型の結晶相が得られやすく、容量及びサイクル特性に優れるものの、高価なリチウム源を多量に使用する必要があるため、リチウム量を遷移金属と同等モル数とすることが求められる。しかしながら、この場合には、容量及びサイクル特性を向上させることは困難である。 By the way, in the nickel-manganese composite oxide described above, when lithium is excessive, a uniform and single layered rock salt type crystal phase is easily obtained, and although the capacity and cycle characteristics are excellent, a large amount of expensive lithium source is used. Therefore, the amount of lithium is required to be the same as the number of moles of the transition metal. However, in this case, it is difficult to improve the capacity and the cycle characteristics.
上記のような事情に鑑み、本発明は、高価で且つ資源的に偏在しているコバルトを使用することなく、また、リチウム量を過剰とすることなく、容量、サイクル特性に優れた正極活物質として有用な複合酸化物を得ることを目的とする。 In view of the above circumstances, the present invention is a positive electrode active material excellent in capacity and cycle characteristics, without using expensive and unevenly distributed resources of cobalt and without increasing the amount of lithium. The purpose is to obtain a complex oxide useful as
本発明者らは上記目的を達成すべく鋭意研究を重ねた結果、二種以上の層状岩塩型構造の結晶相を含有し、そのうち一相の層状岩塩型構造の結晶相は、遷移金属層内格子位置の遷移金属占有率（g3b）が77%以下であるニッケル含有リチウムマンガン複合酸化物が、上記課題を解決することができることを見出した。本発明者らは、このような知見に基づきさらに研究を重ね、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned objects, the inventors of the present invention contain two or more types of crystal phases having a layered rock-salt structure, and one of them has a crystal phase having a layered rock-salt structure in the transition metal layer. It has been found that a nickel-containing lithium manganese composite oxide having a transition metal occupancy (g 3b ) at a lattice position of 77% or less can solve the above problems. The present inventors have conducted further research based on such findings and completed the present invention.
すなわち、本発明は、以下のニッケル含有リチウムマンガン複合酸化物及びその製造方法を包含する。
項１．一般式（1）：
Li1+x(NiyMn1-y)1-xO2 （1）
［式中、x及びyはそれぞれ-0.1<x<0.1、0.4≦y≦0.6を示す。］
で表され、
二種以上の層状岩塩型構造の結晶相を含有し、
そのうち一相の層状岩塩型構造の結晶相（2）は、遷移金属層内格子位置の遷移金属占有率（g3b）が65.0〜77.0%である、ニッケル含有リチウムマンガン複合酸化物。
項２．前記層状岩塩型構造の結晶相（2）は、組成式あたりの遷移金属占有率（gtotal）が67.0〜90.0%である、項１に記載のニッケル含有リチウムマンガン複合酸化物。
項３．前記層状岩塩型構造の結晶相（2）は、格子定数a軸値が2.850〜2.885Åである、項１又は２に記載のニッケル含有リチウムマンガン複合酸化物。
項４． X線回折パターンにおける104面のピークの半価幅が0.21〜2.00°である、項１〜３のいずれか1項に記載のニッケル含有リチウムマンガン複合酸化物。
項５．前記ニッケル含有リチウムマンガン複合酸化物が有する結晶構造の総量を100モル%として、前記層状岩塩型構造の結晶相（2）の存在比率が10〜40モル%である、項１〜４のいずれか1項に記載のニッケル含有リチウムマンガン複合酸化物。
項６．項１〜５のいずれか1項に記載のニッケル含有リチウムマンガン複合酸化物を含むリチウムイオン二次電池用正極活物質。
項７．項６に記載のリチウムイオン二次電池用正極活物質を備える、リチウムイオン二次電池。
項８．項１〜５のいずれか1項に記載のニッケル含有リチウムマンガン複合酸化物の製造方法であって、
（1）マンガン化合物及びニッケル化合物を含む混合水溶液から、アルカリ性条件下にて沈殿物を形成する工程、
（2）前記沈殿物に湿式酸化処理を行う工程、及び
（3）リチウム塩共存下酸化性雰囲気下、500〜980℃で熱処理する工程
を備える、製造方法。
That is, the present invention includes the following nickel-containing lithium manganese composite oxide and a method for producing the same.
Item 1. General formula (1):
Li 1+x (Ni y Mn 1-y ) 1-x O 2 (1)
[In the formula, x and y represent −0.1<x<0.1 and 0.4≦y≦0.6, respectively. ]
Is represented by
Containing a crystalline phase of two or more layered rock salt type structure,
One of the phases, a crystalline phase (2) having a layered rock salt structure, is a nickel-containing lithium manganese composite oxide having a transition metal occupancy (g 3b ) at a lattice position in the transition metal layer of 65.0 to 77.0%.
Item 2. Item 2. The nickel-containing lithium manganese composite oxide according to Item 1, wherein the crystal phase (2) of the layered rock salt type structure has a transition metal occupancy rate (g total ) per composition formula of 67.0 to 90.0%.
Item 3. Item 3. The nickel-containing lithium manganese composite oxide according to Item 1 or 2, wherein the crystal phase (2) of the layered rock salt type structure has a lattice constant a-axis value of 2.850 to 2.885Å.
Item 4. Item 10. The nickel-containing lithium manganese composite oxide according to any one of Items 1 to 3, wherein the full width at half maximum of the 104-plane peak in the X-ray diffraction pattern is 0.21 to 2.00°.
Item 5. Any one of Items 1 to 4, wherein the total amount of the crystal structure of the nickel-containing lithium manganese composite oxide is 100 mol%, and the abundance ratio of the crystal phase (2) of the layered rock salt type structure is 10 to 40 mol %. The nickel-containing lithium manganese composite oxide according to item 1.
Item 6. Item 7. A positive electrode active material for a lithium ion secondary battery, comprising the nickel-containing lithium manganese composite oxide according to any one of Items 1 to 5.
Item 7. Item 7. A lithium ion secondary battery comprising the positive electrode active material for a lithium ion secondary battery according to Item 6.
Item 8. Item 10. A method for producing the nickel-containing lithium manganese composite oxide according to any one of Items 1 to 5,
(1) a step of forming a precipitate under alkaline conditions from a mixed aqueous solution containing a manganese compound and a nickel compound,
(2) A production method comprising a step of subjecting the precipitate to a wet oxidation treatment, and (3) a heat treatment at 500 to 980° C. in an oxidizing atmosphere in the presence of a lithium salt.
本発明によれば、高価で且つ資源的に偏在しているコバルトを使用することなく、また、リチウム量を過剰とすることなく、容量、サイクル特性に優れた正極活物質として有用な複合酸化物を得ることができる。 According to the present invention, a composite oxide useful as a positive electrode active material having excellent capacity and cycle characteristics without using expensive and unevenly distributed resources of cobalt and without excessively increasing the amount of lithium. Can be obtained.
本明細書において、「含有」は、「含む（comprise）」、「実質的にのみからなる（consist essentially of）」、及び「のみからなる（consist of）」のいずれも包含する概念である。また、本明細書において、数値範囲をA〜Bで表記する場合、A以上B以下を示す。 In the present specification, the term “inclusion” is a concept including both “comprise”, “consisting essentially of”, and “consist of”. Further, in the present specification, when the numerical range is represented by A to B, it indicates A or more and B or less.
１．ニッケル含有リチウムマンガン複合酸化物
本発明のニッケル含有リチウムマンガン複合酸化物は、一般式（1）：
Li1+x(NiyMn1-y)1-xO2 （1）
［式中、x及びyはそれぞれ-0.1<x<0.1、0.4≦y≦0.6を示す。］
で表され、
二種以上の層状岩塩型構造の結晶相を含有し、
そのうち一相の層状岩塩型構造の結晶相は、遷移金属層内格子位置の遷移金属占有率（g3b）が77%以下である。
1. Nickel-Containing Lithium Manganese Composite Oxide The nickel-containing lithium manganese composite oxide of the present invention has the general formula (1):
Li 1+x (Ni y Mn 1-y ) 1-x O 2 (1)
[In the formula, x and y represent −0.1<x<0.1 and 0.4≦y≦0.6, respectively. ]
Is represented by
Containing a crystalline phase of two or more layered rock salt type structure,
One of them, the crystal phase of the layered rock-salt type structure, has a transition metal occupancy (g 3b ) at the lattice position in the transition metal layer of 77% or less.
上記一般式（1）において、xは-0.1<x<0.1であり、-0.08<x<0.08がより好ましい。Xが-0.1以下であれば充放電容量の低下をもたらし、0.1以上であれば炭酸リチウム等の不純物相が増え結果として充放電容量低下につながる。 In the general formula (1), x is -0.1<x<0.1, and more preferably -0.08<x<0.08. If X is −0.1 or less, the charge/discharge capacity is lowered, and if 0.1 or more, the impurity phase such as lithium carbonate is increased, resulting in a decrease in the charge/discharge capacity.
上記一般式（1）において、yは0.4≦y≦0.6であり、0.45≦y≦0.55が好ましい。yが0.4未満であると、定比保持のために多量のリチウムが必要になり、コストが増大するうえに、電圧の低下も招く。一方、yが0.6を超えると、充電時の構造安定性が低下するとともに容量が低下する。 In the above general formula (1), y is 0.4≦y≦0.6, preferably 0.45≦y≦0.55. If y is less than 0.4, a large amount of lithium is required to maintain the stoichiometric ratio, resulting in an increase in cost and a decrease in voltage. On the other hand, when y exceeds 0.6, the structure stability during charging and the capacity decrease.
また、本発明のニッケル含有リチウムマンガン複合酸化物は、二種以上の層状岩塩型結晶相を含んでいる。層状岩塩型結晶相を構成する層状岩塩型結晶構造とは、コバルト酸リチウムやニッケル酸リチウムが有するABO2型（Aはアルカリ金属、Bは遷移金属を示す。）の無機化合物に多く出現する結晶構造である。酸化物イオンを介して遷移金属層とリチウム層とが交互に積層した結晶構造であり、充放電に伴って、リチウムイオンの脱離・挿入反応が容易であるといわれている。 Further, the nickel-containing lithium manganese composite oxide of the present invention contains two or more kinds of layered rock salt type crystal phases. The layered rock salt type crystal structure that constitutes the layered rock salt type crystal phase is a crystal that often appears in ABO 2 type (A is an alkali metal, B is a transition metal) inorganic compound of lithium cobalt oxide or lithium nickel oxide. It is a structure. It has a crystal structure in which transition metal layers and lithium layers are alternately laminated via oxide ions, and it is said that desorption/insertion reactions of lithium ions are easy with charge and discharge.
このような層状岩塩型結晶相としては、空間群： Such layered rock-salt type crystal phases include space groups:
に帰属する六方晶層状岩塩型構造の結晶相を少なくとも二種以上含むことが好ましい。本発明のニッケル含有リチウムマンガン複合酸化物は、上記の六方晶層状岩塩型構造の結晶相を二種以上含むことが好ましく、他の岩塩型構造の結晶相（例えば、立方晶岩塩型構造等）を含む混合相であってもよい。混合相である場合、六方晶層状岩塩型構造の結晶相の合計割合は、当該混合相全体を基準として、50〜90質量%が好ましい。また、本発明のニッケル含有リチウムマンガン複合酸化物は、二種以上の六方晶層状岩塩型構造の結晶相のみからなる構成も採用し得る。 It is preferable to include at least two kinds of crystal phases having a hexagonal layered rock salt structure belonging to The nickel-containing lithium manganese composite oxide of the present invention preferably contains two or more kinds of crystal phases of the above-mentioned hexagonal layered rock salt type structure, and crystal phases of other rock salt type structures (for example, cubic rock salt type structure) It may be a mixed phase containing. In the case of the mixed phase, the total proportion of the crystal phases of the hexagonal layered rock salt type structure is preferably 50 to 90 mass% based on the entire mixed phase. Further, the nickel-containing lithium-manganese composite oxide of the present invention may also have a constitution in which it is composed of only two or more hexagonal layered rock salt type crystal phases.
図１は六方晶層状岩塩型構造の結晶相を模式的に示す図面である。この構造においては6c位置に存在する酸化物イオン相を介して3a位置に存在するリチウム層と3b位置に存在する遷移金属層とが交互に積層している。コバルト酸リチウムでは比較的このような理想構造に近いものが得られるが、本発明のニッケル含有リチウムマンガン複合酸化物においては、遷移金属層内遷移金属占有率等の異なる二種以上の結晶相が共存している。 FIG. 1 is a drawing schematically showing a crystal phase having a hexagonal layered rock salt structure. In this structure, a lithium layer at the 3a position and a transition metal layer at the 3b position are alternately laminated via the oxide ion phase at the 6c position. With lithium cobalt oxide, a compound having a structure relatively close to such an ideal structure can be obtained, but in the nickel-containing lithium manganese composite oxide of the present invention, two or more crystal phases having different transition metal occupancy in the transition metal layer are present. Coexist.
このような遷移金属層内遷移金属占有率等の異なる結晶相としては、（1）主相として、遷移金属層内の3b位置遷移金属占有率が90.0%以上の結晶相、（2）副相として、遷移金属層内格子位置（3b位置）の遷移金属占有率（遷移金属層内の3b位置遷移金属占有率；g3b）が77.0%以下の結晶相が挙げられる。 Such crystal phases having different transition metal occupancy in the transition metal layer include (1) a main phase, a crystal phase in which the 3b position transition metal occupancy in the transition metal layer is 90.0% or more, and (2) a sub-phase. Examples of the crystalline phase include a transition metal occupancy at the lattice position (3b position) in the transition metal layer (transition metal occupancy at the 3b position in the transition metal layer; g 3b ) of 77.0% or less.
このうち、副相として存在している層状岩塩型構造の結晶相（以下、「層状岩塩型構造の結晶相（2）」と称することもある）については、遷移金属層内の3b位置遷移金属占有率（g3b）が65.0〜77.0%であることが必須である。この層状岩塩型構造の結晶相（2）は、通常得られる層状岩塩型結晶構造の結晶相と比較すると、遷移金属層内の3b位置遷移金属占有率が低い結晶相であり、理由は明らかではないが、この副相の存在により、高容量且つサイクル特性に優れた特性を得ることができる。 Of these, the crystal phase of the layered rock-salt structure existing as a sub-phase (hereinafter, also referred to as “the crystal phase of the layered rock-salt structure (2)”) is a 3b position transition metal in the transition metal layer. It is essential that the occupancy rate (g 3b ) is 65.0 to 77.0%. The crystal phase (2) of the layered rock-salt type structure is a crystal phase having a lower 3b position transition metal occupancy in the transition metal layer than the crystal phase of the normally obtained layered rock-salt type crystal structure, and the reason is not clear. Although not present, the presence of this subphase makes it possible to obtain high capacity and excellent cycle characteristics.
この層状岩塩型構造の結晶相（2）における、遷移金属層内の3b位置遷移金属占有率は65.0〜77.0%、好ましくは70.0〜76.0%である。層状岩塩型構造の結晶相（2）において、遷移金属層内の3b位置遷移金属占有率が65.0%未満では、結晶相(2)に含まれる充放電特性の悪いLi2MnO3成分が多くなりすぎるため、充放電特性が悪化する。層状岩塩型構造の結晶相（2）において、遷移金属層内の3b位置遷移金属占有率が77.0%をこえると、容量及びサイクル特性が低下する。 In the crystal phase (2) of this layered rock salt structure, the 3b position transition metal occupancy in the transition metal layer is 65.0 to 77.0%, preferably 70.0 to 76.0%. In the crystalline phase (2) of the layered rock salt structure, if the 3b position transition metal occupancy in the transition metal layer is less than 65.0%, the Li 2 MnO 3 component with poor charge/discharge characteristics contained in the crystalline phase (2) increases. Therefore, the charging/discharging characteristics are deteriorated. In the crystal phase (2) of the layered rock-salt type structure, when the 3b position transition metal occupancy in the transition metal layer exceeds 77.0%, the capacity and cycle characteristics deteriorate.
また、層状岩塩型構造の結晶相（2）は、遷移金属層内の3b位置遷移金属占有率が小さいため、3a位置遷移金属占有率と3b位置のそれとの和に相当する、組成式あたりの遷移金属占有率（gtotal）も結果的に小さくなる。このことから、層状岩塩型構造の結晶相（2）は、容量、サイクル特性等の観点から、組成式あたりの遷移金属占有率（gtotal）は67.0〜90.0%が好ましく、75.0〜88.0%がより好ましい。 In addition, since the crystal phase (2) of the layered rock-salt structure has a small 3b position transition metal occupancy in the transition metal layer, it corresponds to the sum of the 3a position transition metal occupancy and the 3b position transition metal per composition formula. As a result, the transition metal occupancy (g total ) also becomes small. From this, the crystal phase (2) of the layered rock salt type structure, from the viewpoint of capacity, cycle characteristics, etc., the transition metal occupancy rate per composition formula (g total ) is preferably 67.0 to 90.0%, and 75.0 to 88.0%. More preferable.
また、層状岩塩型構造の結晶相（2）は、遷移金属層内の3b位置遷移金属占有率が小さいため、遷移金属層に空孔が多く格子定数は小さくなりやすい。このことから、層状岩塩型構造の結晶相（2）は、容量、サイクル特性等の観点から、格子定数a軸値は2.850〜2.885Åが好ましく、2.870〜2.883Åがより好ましい。同様に、格子体積Vは101.00〜103.00Å3が好ましく、101.50〜102.95Å3がより好ましい。本明細書における格子定数a及び格子体積Vは、六方晶層状岩塩型格子として仮定して算出された値を意味する。 Further, in the crystal phase (2) having a layered rock-salt structure, since the 3b position transition metal occupancy in the transition metal layer is small, the transition metal layer tends to have many vacancies and a small lattice constant. From this, the crystal phase (2) of the layered rock salt type structure has a lattice constant a-axis value of preferably 2.850 to 2.885Å, more preferably 2.870 to 2.883Å, from the viewpoint of capacity, cycle characteristics and the like. Similarly, lattice volume V is preferably 101.00~103.00Å 3, 101.50~102.95Å 3 is more preferable. The lattice constant a and the lattice volume V in the present specification mean values calculated assuming a hexagonal layered rock salt lattice.
次に、主相として存在している層状岩塩型構造の結晶相（以下、「層状岩塩型構造の結晶相（1）」と称することもある）については、遷移金属層内の3b位置遷移金属占有率が90.0%以上であることが好ましい。この層状岩塩型構造の結晶相（1）は、通常得られる層状岩塩型結晶構造の結晶相と同一又は類似の結晶相である。この層状岩塩型構造の結晶相（1）における、遷移金属層内の3b位置遷移金属占有率は90.0〜100%が好ましく、90.2〜95.0%がより好ましい。 Next, regarding the crystal phase of the layered rock salt type structure that exists as the main phase (hereinafter, also referred to as “the crystal phase of the layered rock salt type structure (1)”), the 3b position transition metal in the transition metal layer The occupancy rate is preferably 90.0% or more. The crystal phase (1) of this layered rock salt type structure is the same or similar to the crystal phase of the layered rock salt type crystal structure that is usually obtained. In the crystal phase (1) of this layered rock salt type structure, the 3b position transition metal occupancy in the transition metal layer is preferably 90.0 to 100%, more preferably 90.2 to 95.0%.
また、層状岩塩型構造の結晶相（1）は、遷移金属層内の3b位置遷移金属占有率は層状岩塩型構造の結晶相（2）と比較すると大きいため、3a位置遷移金属占有率と3b位置のそれとの和に相当する、組成式あたりの遷移金属占有率（gtotal）も結果的に大きくなる。このことから、層状岩塩型構造の結晶相（1）は、組成式あたりの遷移金属占有率（gtotal）は99.5〜110.0%が好ましく、100.0〜105.0%がより好ましい。 In addition, the crystal phase (1) of the layered rock-salt type structure has a larger 3b position transition metal occupancy in the transition metal layer than the crystal phase (2) of the layered rock salt type structure. The transition metal occupancy rate (g total ) per composition formula, which corresponds to the sum of the position and that, also increases as a result. From this, in the crystal phase (1) of the layered rock salt type structure, the transition metal occupancy rate (g total ) per composition formula is preferably 99.5 to 110.0%, and more preferably 100.0 to 105.0%.
また、層状岩塩型構造の結晶相（1）は、遷移金属層内の3b位置遷移金属占有率は層状岩塩型構造の結晶相（2）と比較すると大きいため、遷移金属層に空孔が少なく格子定数は大きくなりやすい。このことから、層状岩塩型構造の結晶相（1）は、格子定数a軸値は2.886〜2.900Åが好ましく、2.888〜2.895Åがより好ましい。同様に、格子体積Vは103.10〜105.00Å3が好ましく、103.20〜104.00Å3がより好ましい。本明細書における格子定数a及び格子体積Vは、六方晶層状岩塩型格子として仮定して算出された値を意味する。 In addition, the crystal phase (1) of the layered rock-salt type structure has a larger occupancy ratio of the transition metal at the 3b position in the transition metal layer than the crystal phase (2) of the layered rock-salt type structure. The lattice constant tends to increase. From this, the crystal phase (1) of the layered rock salt structure has a lattice constant a-axis value of preferably 2.886 to 2.900Å, more preferably 2.888 to 2.895Å. Similarly, lattice volume V is preferably 103.10~105.00Å 3, 103.20~104.00Å 3 is more preferable. The lattice constant a and the lattice volume V in the present specification mean values calculated assuming a hexagonal layered rock salt lattice.
上記した層状岩塩型構造の結晶相（1）及び層状岩塩型構造の結晶相（2）の存在量については、層状岩塩型構造の結晶相（1）が主相で層状岩塩型構造の結晶相（2）が副相であるところ、容量、サイクル特性等の観点から、本発明のニッケル含有リチウムマンガン複合酸化物が有する結晶構造の総量を100モル%として、層状岩塩型構造の結晶相（2）の存在比率は10〜40モル%が好ましく、15〜35モル%がより好ましい。また、同様に、層状岩塩型構造の結晶相（1）の存在比率は60〜90モル%が好ましく、65〜85モル%がより好ましい。 Regarding the abundances of the crystal phase (1) of the layered rock salt structure and the crystal phase (2) of the layered rock salt type structure, the crystal phase of the layered rock salt type structure (1) is the main phase and the crystal phase of the layered rock salt type structure is Where (2) is a subphase, from the viewpoint of capacity, cycle characteristics, etc., the total amount of the crystal structure of the nickel-containing lithium manganese composite oxide of the present invention is 100 mol %, and the crystal phase of the layered rock salt type structure (2 The abundance ratio of) is preferably 10 to 40 mol %, more preferably 15 to 35 mol %. Similarly, the proportion of the crystal phase (1) having the layered rock salt structure is preferably 60 to 90 mol%, more preferably 65 to 85 mol%.
なお、本発明のニッケル含有リチウムマンガン複合酸化物は、本発明の効果に重大な影響を及ぼさない範囲の立方晶岩塩型酸化物（NiO等）、炭酸リチウムや水酸化リチウム等のリチウム塩、他のニッケルあるいはマンガン化合物（それらの水和物及び複合化合物も含む）等の不純物相を含んでいてよく、その量については本発明のニッケルマンガン複合酸化物の総量を100モル%として、10モル%以下、特に5モル%以下が好ましい。 The nickel-containing lithium manganese composite oxide of the present invention is a cubic rock salt type oxide (NiO or the like), a lithium salt such as lithium carbonate or lithium hydroxide, etc., which does not seriously affect the effect of the present invention. Of nickel or manganese compound (including hydrates and complex compounds thereof), etc. may be included, and the amount thereof is 10 mol% based on the total amount of the nickel-manganese composite oxide of the present invention being 100 mol %. It is particularly preferably 5 mol% or less.
また、本発明のニッケル含有リチウムマンガン複合酸化物は、X線回折パターンにおいて2θ=45°付近にある104面のピークは、容量、サイクル特性等の観点から、結晶性をやや低めとすることが好ましく、その半価幅は0.21〜2.00°が好ましく、0.22〜1.00°がより好ましい。 Further, the nickel-containing lithium manganese composite oxide of the present invention, the peak of 104 plane in the vicinity of 2θ = 45° in the X-ray diffraction pattern, from the viewpoint of capacity, cycle characteristics, etc., the crystallinity may be rather low. The full width at half maximum is preferably 0.21 to 2.00°, more preferably 0.22 to 1.00°.
以上の特徴から、本発明のニッケル含有リチウムマンガン複合酸化物は、主相である層状岩塩型構造の結晶相（1）のみからなる従来物質よりも優れた容量及びサイクル特性を示す。 From the above characteristics, the nickel-containing lithium-manganese composite oxide of the present invention exhibits more excellent capacity and cycle characteristics than the conventional substance consisting only of the crystal phase (1) having the layered rock salt type structure as the main phase.
２．リチウムイオン二次電池用正極活物質及びリチウムイオン二次電池
上記した本発明のニッケル含有リチウムマンガン複合酸化物は、リチウムイオン二次電池用正極活物質として用いることができる。このような本発明の正極活物質に、公知の導電剤及びバインダーと混合することで作製した正極合剤をアルミニウム、ニッケル、ステンレス、カーボンクロス等の正極集電体に担持させることで、正極を製造することができる。導電剤としては、例えば、黒鉛、コークス類、カーボンブラック、針状カーボン等の炭素材料を用いることができる。負極活物質としても特に限定的ではなく、例えば、金属リチウム、黒鉛、Si-SiO系負極、LTO（Li4Ti5O12）系負極等が挙げられる。これらの負極活物質についても、必要に応じて、導電剤、バインダー等を用いて、アルミニウム、銅、ニッケル、ステンレス、カーボン等からなる負極集電体に担持させて、負極を製造することができる。電解質としては特に限定的ではなく、LiPF6等を電解質塩とし、炭酸エチル（EC）や炭酸ジメチル（DMC）等の各種溶媒に溶解させた有機電解液、Li2S-P2S5、Li2S-GeS2-P2S5、Li2S-SiS2-Li2PO4等の無機硫化物系固体電解質、リチウムイオン導電性を有する高分子ポリマー等が挙げられる。セパレータとしては特に限定的ではなく、ポリエチレン、ポリプロピレン等が挙げられる。
2. Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery The nickel-containing lithium manganese composite oxide of the present invention described above can be used as a positive electrode active material for a lithium ion secondary battery. Such a positive electrode active material of the present invention, by supporting a positive electrode mixture prepared by mixing a known conductive agent and a binder on a positive electrode current collector such as aluminum, nickel, stainless steel, carbon cloth, a positive electrode It can be manufactured. As the conductive agent, for example, carbon materials such as graphite, cokes, carbon black, and needle-shaped carbon can be used. The negative electrode active material is not particularly limited, and examples thereof include metallic lithium, graphite, Si—SiO based negative electrodes, and LTO (Li 4 Ti 5 O 12 ) based negative electrodes. Also for these negative electrode active materials, a negative electrode can be manufactured by using a conductive agent, a binder, etc., if necessary, and supporting them on a negative electrode current collector made of aluminum, copper, nickel, stainless steel, carbon, or the like. .. The electrolyte is not particularly limited, and LiPF 6 or the like is used as an electrolyte salt and dissolved in various solvents such as ethyl carbonate (EC) or dimethyl carbonate (DMC), Li 2 SP 2 S 5 , Li 2 S Examples thereof include inorganic sulfide-based solid electrolytes such as -GeS 2 -P 2 S 5 , Li 2 S-SiS 2 -Li 2 PO 4 , and high molecular polymers having lithium ion conductivity. The separator is not particularly limited, and examples thereof include polyethylene and polypropylene.
３．ニッケル含有リチウムマンガン複合酸化物の製造方法
また本発明は、さらに上述した本発明のニッケル含有リチウムマンガン複合酸化物の製造方法を包含する。本発明のニッケル含有リチウムマンガン複合酸化物の製造方法は、
（1）マンガン化合物及びニッケル化合物を含む混合水溶液から、アルカリ性条件下にて沈殿物を形成する工程、
（2）前記沈殿物に湿式酸化処理を行う工程、及び
（3）リチウム塩共存下酸化性雰囲気下、500〜980℃で熱処理する工程
を備える。
3. Method for Producing Nickel-Containing Lithium Manganese Composite Oxide The present invention further includes the method for producing the nickel-containing lithium manganese composite oxide of the present invention described above. The method for producing a nickel-containing lithium manganese composite oxide of the present invention,
(1) a step of forming a precipitate under alkaline conditions from a mixed aqueous solution containing a manganese compound and a nickel compound,
(2) A step of subjecting the precipitate to a wet oxidation treatment, and (3) a step of heat-treating at 500 to 980° C. in an oxidizing atmosphere in the presence of a lithium salt.
（３−１）工程（1）
使用するマンガン化合物としては、特に限定はなく、塩化マンガン（II）、硫酸マンガン（II）、酢酸マンガン（II）、酢酸マンガン（III）、硝酸マンガン（II）、アセチル酢酸マンガン（II）、アセチル酢酸マンガン（III）、過マンガン酸カリウム（VII）等水和物も含め、公知のものを広く使用することが可能である。また酸化マンガンや金属マンガンも適切な酸で溶解させることにより水溶性塩として用いることができる。
(3-1) Step (1)
The manganese compound used is not particularly limited, and manganese chloride (II), manganese sulfate (II), manganese acetate (II), manganese acetate (III), manganese nitrate (II), acetyl manganese acetate (II), acetyl acetate It is possible to widely use known ones including hydrates such as manganese (III) acetate and potassium permanganate (VII). Further, manganese oxide and metallic manganese can also be used as a water-soluble salt by dissolving them with a suitable acid.
使用するニッケル化合物としても特に限定はなく、硝酸ニッケル（II）、酢酸ニッケル（II）、塩化ニッケル（II）、硫酸ニッケル（II）等水和物も含め、公知のものを広く使用することができる。また酸化ニッケルや金属ニッケルも適切な酸で溶解させることにより水溶性塩として用いることができる。 The nickel compound to be used is not particularly limited, and widely known ones can be widely used, including nickel nitrate (II), nickel acetate (II), nickel chloride (II), nickel sulfate (II) and the like hydrates. it can. Further, nickel oxide or metallic nickel can also be used as a water-soluble salt by dissolving with a suitable acid.
用いるニッケル化合物及びマンガン化合物の配合比は目的とする本発明のニッケル含有リチウムマンガン複合酸化物の配合比と同一とすることができる。 The blending ratio of the nickel compound and the manganese compound used can be the same as the intended blending ratio of the nickel-containing lithium manganese composite oxide of the present invention.
マンガン化合物及びニッケル化合物を含む混合水溶液における金属塩濃度については特に限定されず、均一な混合水溶液を形成でき、且つ円滑に共沈物を形成できるように適宜決めることができる。通常ニッケル化合物及びマンガン化合物の合計濃度は0.01〜5mol/lが好ましく、0.1〜2mol/lがより好ましい。 The metal salt concentration in the mixed aqueous solution containing the manganese compound and the nickel compound is not particularly limited, and can be appropriately determined so that a uniform mixed aqueous solution can be formed and a coprecipitate can be smoothly formed. Usually, the total concentration of the nickel compound and the manganese compound is preferably 0.01 to 5 mol/l, more preferably 0.1 to 2 mol/l.
マンガン化合物及びニッケル化合物を含む混合水溶液の溶媒としては水単独の他、メタノール、エタノール等の水溶性アルコールを含む水−アルコール混合溶媒を用いることもできる。水溶性アルコールはマンガン源として過マンガン酸カリウムを用いる際の沈殿材としても用いることができる。また、水溶性アルコールは0℃以下の低温滴下時の不凍液として用いることもでき、0℃を下回る温度での沈殿形成が可能となる。水溶性アルコールを使用する場合の使用量は目的とする沈殿形成温度等によって適宜設定することができるが、通常水100質量部に対して水溶性アルコールは50重量部以下（特に5〜45質量部）とすることができる。 As the solvent of the mixed aqueous solution containing the manganese compound and the nickel compound, not only water but also a water-alcohol mixed solvent containing a water-soluble alcohol such as methanol or ethanol can be used. The water-soluble alcohol can also be used as a precipitation material when using potassium permanganate as a manganese source. Further, the water-soluble alcohol can also be used as an antifreeze solution at low temperature dropping at 0°C or lower, and it becomes possible to form a precipitate at a temperature below 0°C. The amount of water-soluble alcohol to be used can be appropriately set depending on the desired precipitation formation temperature and the like, but usually 50 parts by weight or less of water-soluble alcohol per 100 parts by weight of water (especially 5 to 45 parts by weight). ) Can be.
マンガン化合物及びニッケル化合物を含む混合水溶液から沈殿物（共沈物）を形成させる方法としては、該混合水溶液をアルカリ性にすることが挙げられる。良質な沈殿物を形成する条件は、混合水溶液に含まれる各化合物種や濃度により異なるため一概には言えないが、通常pH8以上が好ましく、pH11〜14がより好ましい。 Examples of a method for forming a precipitate (coprecipitate) from a mixed aqueous solution containing a manganese compound and a nickel compound include making the mixed aqueous solution alkaline. The condition for forming a high-quality precipitate cannot be generally stated because it varies depending on each compound species and concentration contained in the mixed aqueous solution, but usually pH 8 or higher is preferable, and pH 11 to 14 is more preferable.
マンガン化合物及びニッケル化合物を含む混合水溶液をアルカリ性にする方法には、特に限定はなく、マンガン化合物及びニッケル化合物を含む混合水溶液とアルカリ溶液とを混合することができる。この際の混合方法としては、公知の混合方法を広く採用することが可能であり、特に限定はない。例えば、アルカリ溶液に対して該混合水溶液を徐々に添加することができる。アルカリ溶液を形成するアルカリ源としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、水酸化リチウム（それらの水和物を含む）等を用いることができる。アルカリ濃度に関しては、例えば0.1〜20mol/lが好ましく、0.3〜10mol/lがより好ましい。またアルカリ溶液に上述した水溶性アルコールを添加して、水−アルコール混合溶媒とすることもできる。 The method for making the mixed aqueous solution containing the manganese compound and the nickel compound alkaline is not particularly limited, and the mixed aqueous solution containing the manganese compound and the nickel compound can be mixed with the alkaline solution. As a mixing method at this time, a known mixing method can be widely adopted, and there is no particular limitation. For example, the mixed aqueous solution can be gradually added to the alkaline solution. As the alkali source forming the alkali solution, for example, sodium hydroxide, potassium hydroxide, ammonia, lithium hydroxide (including hydrates thereof), or the like can be used. Regarding the alkali concentration, for example, 0.1 to 20 mol/l is preferable, and 0.3 to 10 mol/l is more preferable. Alternatively, the water-soluble alcohol described above may be added to the alkaline solution to prepare a water-alcohol mixed solvent.
沈殿形成の際には、例えば、恒温槽等の温度を調整及び保持することが可能な公知の容器を用いて、中和熱による材料の変質緩和のために温度管理を行うことが好ましい。経験的には、低温で沈殿形成させるほど遷移金属分布の均一な沈殿物が形成されやすい傾向がある。このため、アルカリ溶液の温度は-50℃〜+30℃が好ましく、-20℃〜+20℃がより好ましい。ここで、設定温度を0℃以下とする場合には、アルカリ溶液に不凍液として上記した水溶性アルコールを入れておくことが好ましい。 At the time of forming the precipitate, for example, it is preferable to use a known container capable of adjusting and holding the temperature, such as a constant temperature bath, to control the temperature for mitigating alteration of the material due to heat of neutralization. Empirically, the lower the temperature of the precipitate formation, the more easily the precipitate having a uniform transition metal distribution is formed. Therefore, the temperature of the alkaline solution is preferably -50°C to +30°C, more preferably -20°C to +20°C. Here, when the set temperature is set to 0° C. or lower, it is preferable to add the above-mentioned water-soluble alcohol as an antifreeze solution to the alkaline solution.
上記沈殿形成反応時には、アルカリ溶液に対してマンガン化合物及びニッケル化合物を含む混合水溶液を徐々に滴下しつつ添加していくことも、中和熱発生に伴う副反応抑制の観点からは好ましい。滴下時間は特に限定されるものでないが、通常1〜10時間が好ましく、2〜5時間がより好ましい。 During the precipitation formation reaction, it is also preferable to gradually add a mixed aqueous solution containing a manganese compound and a nickel compound to the alkaline solution from the viewpoint of suppressing side reactions due to the heat of neutralization. Although the dropping time is not particularly limited, it is usually preferably 1 to 10 hours, more preferably 2 to 5 hours.
（３−２）工程（2）
工程（2）において、上記工程（1）において得られた沈殿物に、湿式酸化処理を施す。工程（2）は沈殿物を含むアルカリ溶液に空気や酸素等の酸化性気体を吹き込む（バブリングする）ことにより沈殿を酸化熟成してリチウムとの反応性の高い前駆体を作ることができる。吹き込む気体は、酸素が含まれていれば制限はなく、空気でもよいが、酸化時間の短縮の観点から、酸素が好ましい。酸素の場合、通常用いるボンベのみならず、工業用の酸素発生機を用いることもできる。湿式酸化の温度も特に限定はなく、例えば、0〜150℃、特に10〜100℃とすることができる。湿式酸化時間は、反応を充分に進行させるという観点から、長いほどよいが1時間以上が好ましく、24時間以上がより好ましく、48時間以上がさらに好ましい。
(3-2) Step (2)
In step (2), the precipitate obtained in step (1) is subjected to wet oxidation treatment. In the step (2), an oxidizing gas such as air or oxygen is blown (bubbled) into an alkaline solution containing a precipitate to oxidize and aged the precipitate to form a precursor having high reactivity with lithium. The gas to be blown is not limited as long as it contains oxygen, and may be air, but oxygen is preferable from the viewpoint of shortening the oxidation time. In the case of oxygen, not only a commonly used cylinder but also an industrial oxygen generator can be used. The temperature of wet oxidation is not particularly limited, and may be, for example, 0 to 150°C, particularly 10 to 100°C. From the viewpoint of allowing the reaction to proceed sufficiently, the wet oxidation time is preferably longer, but is preferably 1 hour or longer, more preferably 24 hours or longer, and further preferably 48 hours or longer.
（３−３）工程（3）
工程（3）において、上記工程（2）において得られた熟成物に、リチウム塩共存下で熱処理を行う。ここで、上記水溶性塩類由来の不純物低減という観点からは、リチウム塩共存下での熱処理を行う前に、上記工程（2）において得られた熟成物を蒸留水等で洗浄し、塩類を除去したうえで濾過することが好ましい。また、リチウム塩共存下で熱処理を行う際には、上記のようにして塩類を除去した熟成物にリチウム塩を添加し、熱処理用原料としてリチウム塩共存下酸化性雰囲気下で、500〜980℃で熱処理することが好ましい。もちろん上記工程（2）で得られた反応物（熟成物）にそのままリチウム塩を添加し、熱処理用原料としてリチウム塩共存下酸化性雰囲気下で、500〜980℃で熱処理することもできる。
(3-3) Step (3)
In step (3), the aged product obtained in step (2) is heat-treated in the presence of a lithium salt. Here, from the viewpoint of reducing impurities derived from the water-soluble salts, the aged product obtained in the step (2) is washed with distilled water or the like to remove salts before the heat treatment in the presence of a lithium salt. Then, it is preferable to filter. When heat treatment is carried out in the presence of a lithium salt, a lithium salt is added to the aged product from which salts have been removed as described above, in the presence of a lithium salt as a raw material for heat treatment in an oxidizing atmosphere at 500 to 980°C. It is preferable to heat-treat. Of course, it is also possible to add a lithium salt as it is to the reaction product (aged product) obtained in the above step (2) and heat-treat it as a raw material for heat treatment at 500 to 980° C. in the presence of a lithium salt in an oxidizing atmosphere.
熱処理の際に熟成物とリチウム塩とを共存させるための具体的な方法としては、公知の手法を用いることができ、特に限定はないが、例えば、必要に応じて塩類を除去した熟成物とリチウム塩とを混合する方法を挙げることができる。 As a specific method for allowing the aged product and the lithium salt to coexist during the heat treatment, a known method can be used, and there is no particular limitation, for example, an aged product from which salts have been removed as necessary. The method of mixing with a lithium salt can be mentioned.
また、熱処理用原料としては、乾燥させた熟成物を用いてもよい。乾燥させた熟成物を使用する場合には、乾燥時に残留アルカリにより固結し、リチウム塩との均一混合が困難になることを回避しやすいという観点から、乾燥前に熟成物とリチウム塩とを混合することが好ましい。 A dried aged product may be used as the raw material for heat treatment. In the case of using the dried aged product, the aged product and the lithium salt are combined with each other before drying from the viewpoint that it is easily solidified by residual alkali during drying and it is easy to avoid uniform mixing with a lithium salt. Mixing is preferred.
リチウム塩としては、公知のリチウム塩を広く使用することが可能であり、特に限定はない。具体的には、安価な炭酸リチウム、熟成物との反応性の高い水酸化リチウム以外に、酢酸リチウム、硝酸リチウム、塩化リチウムや、これらの水和物等を用いることができる。また上記リチウム塩に加えて酸化剤として過塩素酸リチウム及びその水和物を用いることもできる。これらのリチウム塩は、単独で用いることもでき、2種以上を組合せて用いることもできる。 A wide variety of known lithium salts can be used as the lithium salt, and there is no particular limitation. Specifically, in addition to inexpensive lithium carbonate and lithium hydroxide having high reactivity with an aged product, lithium acetate, lithium nitrate, lithium chloride, hydrates thereof, and the like can be used. In addition to the above lithium salt, lithium perchlorate and its hydrate can be used as an oxidizing agent. These lithium salts may be used alone or in combination of two or more.
熟成物に対するリチウム塩の添加量としては、熟成物内のニッケル及びマンガン量のモル数に対するリチウムモル量（Li/(Ni+Mn)比）を、目的物の組成にあわせて調節することが好ましい。つまり、一般式（1）中のx値が-0.1<x<0.1であるため、熟成物内のニッケル及びマンガン量のモル数に対するリチウムモル量（Li/(Ni+Mn)比）は0.82〜1.22が好ましく、0.86〜1.17がより好ましい。なお、Li量を過剰量とすると、ニッケル含有リチウムマンガン複合酸化物には均一且つ単独の結晶が得られやすく、二種以上の層状岩塩型構造の結晶相を含有する本発明のニッケル含有リチウムマンガン複合酸化物は得られにくい。 As the amount of the lithium salt added to the aged product, it is preferable to adjust the lithium molar amount (Li/(Ni+Mn) ratio) to the number of moles of nickel and manganese in the aged product according to the composition of the target product. .. That is, since the x value in the general formula (1) is -0.1<x<0.1, the lithium molar amount (Li/(Ni+Mn) ratio) relative to the molar amount of nickel and manganese in the aged product is 0.82 to 1.22 is preferable, and 0.86 to 1.17 is more preferable. When the amount of Li is excessive, it is easy to obtain a uniform and single crystal in the nickel-containing lithium manganese composite oxide, and the nickel-containing lithium manganese of the present invention containing a crystal phase having two or more layered rock salt structures. Complex oxides are difficult to obtain.
ここで、リチウム塩が水に不溶の場合、乾式混合後、振動ミル等でよく粉砕すること、水溶性の場合はリチウム塩を含む水溶液中に沈殿を十分に分散後、ミキサーにかけて均一なスラリーを作製することが好ましい。スラリー等は、乾燥機により乾燥させ、必要に応じて再度粉砕処理を行うことができる。これにより、熟成物とリチウム塩との混合物を均一な色調にしたり、粗大粒子を含ませないことでより反応性を向上させたりすることも可能である。また粉砕前の混合の方法も乾式でそのまま混合することもできるが、リチウム塩をいったん水溶液としてそこに熟成物を加えて乾燥して混合物を得ることもでき、この際の水溶液の濃度は、通常、0.1〜10mol/lとすることができる。乾燥温度は、スラリー粘度をより上昇させ、熟成物とリチウム塩とをより均一に混合させる観点から100℃以下が好ましく、60℃以下がより好ましい。また、乾燥の際には、真空や凍結乾燥等を用いることもできる。 Here, when the lithium salt is insoluble in water, after dry mixing, pulverize well with a vibration mill or the like, and when water-soluble, sufficiently disperse the precipitate in an aqueous solution containing a lithium salt, and then mix with a mixer to form a uniform slurry. It is preferable to make them. The slurry and the like can be dried by a dryer and can be pulverized again if necessary. As a result, the mixture of the aged product and the lithium salt can be made to have a uniform color tone, and the reactivity can be further improved by not containing coarse particles. The mixing method before pulverization can also be carried out as it is by a dry method as it is, but it is also possible to once prepare an aqueous solution of a lithium salt and add an aged product thereto to obtain a mixture, and the concentration of the aqueous solution at this time is usually , 0.1 to 10 mol/l. The drying temperature is preferably 100°C or lower, more preferably 60°C or lower, from the viewpoint of further increasing the slurry viscosity and mixing the aged product and the lithium salt more uniformly. In addition, vacuum, freeze-drying, or the like can be used at the time of drying.
熱処理方法は、熱を加える処理であれば特に限定はなく、公知の方法を広く採用することが可能である。なかでも、簡便に熱処理を行うことが可能であるという観点から、焼成処理を行うのが好適である。熱処理は、酸化性雰囲気下にて行う。本明細書において酸化性雰囲気にて熱処理を行うとは、大気中、酸素気流中等の酸素を含む雰囲気にて熱処理を行うことを意味する。熱処理を酸化性雰囲気下で行うことにより、本発明のニッケル含有リチウムマンガン複合酸化物における格子パラメータ（格子定数、格子体積等）や、遷移金属層内格子位置の遷移金属占有率（g3b）、組成式あたりの遷移金属占有率（gtotal）等を、上述した数値範囲とすることができ、ひいては、本発明のニッケル含有リチウムマンガン複合酸化物を得ることが可能となる。 The heat treatment method is not particularly limited as long as it is a treatment of applying heat, and widely known methods can be adopted. Among them, it is preferable to perform the baking treatment from the viewpoint that the heat treatment can be easily performed. The heat treatment is performed in an oxidizing atmosphere. In the present specification, performing heat treatment in an oxidizing atmosphere means performing heat treatment in an atmosphere containing oxygen, such as in the air or in an oxygen stream. By performing the heat treatment in an oxidizing atmosphere, the lattice parameter (lattice constant, lattice volume, etc.) in the nickel-containing lithium manganese composite oxide of the present invention, the transition metal occupancy (g 3b ) at the lattice position in the transition metal layer, The transition metal occupancy rate (g total ) per composition formula can be set within the above-mentioned numerical range, and by extension, the nickel-containing lithium manganese composite oxide of the present invention can be obtained.
熱処理温度は、500〜980℃、好ましくは600〜950℃、より好ましくは750〜900℃である。熱処理温度が500℃未満では、得られるニッケル含有リチウムマンガン複合酸化物の電解液との反応性が過多になり、サイクル特性が低下する。熱処理温度が980℃をこえると、ニッケル含有リチウムマンガン複合酸化物には均一且つ単独の結晶が得られ、二種以上の層状岩塩型構造の結晶相を含有する本発明のニッケル含有リチウムマンガン複合酸化物は得られず、容量及びサイクル特性が悪化する。なお、本明細書において、熱処理温度とは、熱処理中の最高到達温度を意味する。 The heat treatment temperature is 500 to 980°C, preferably 600 to 950°C, more preferably 750 to 900°C. When the heat treatment temperature is lower than 500°C, the reactivity of the obtained nickel-containing lithium manganese composite oxide with the electrolytic solution becomes excessive and the cycle characteristics deteriorate. When the heat treatment temperature exceeds 980° C., uniform and independent crystals are obtained in the nickel-containing lithium manganese composite oxide, and the nickel-containing lithium manganese composite oxide of the present invention containing two or more kinds of crystal phases having a layered rock salt structure is formed. No product is obtained, and the capacity and cycle characteristics deteriorate. In the present specification, the heat treatment temperature means the highest temperature reached during the heat treatment.
熱処理時間については、充分な反応を行うという観点から、上記熱処理温度範囲内の温度に保持した状態で、30分以上が好ましく、1時間以上がより好ましい。熱処理時間の上限については特に限定はないが、製造コストの上昇を抑えるという観点から、100時間以下が好ましく、50時間以下がより好ましい。 The heat treatment time is preferably 30 minutes or more, and more preferably 1 hour or more, in the state of being kept at a temperature within the heat treatment temperature range, from the viewpoint of sufficient reaction. The upper limit of the heat treatment time is not particularly limited, but from the viewpoint of suppressing an increase in manufacturing cost, 100 hours or less is preferable, and 50 hours or less is more preferable.
熱処理後、必要に応じて、より充放電性に優れたニッケル含有リチウムマンガン複合酸化物を得るために、工程（3）を複数回、例えば2〜3回繰り返すこともできる。また、必要に応じて、得られた熱処理物を粉砕することもできる。 After the heat treatment, the step (3) can be repeated a plurality of times, for example, 2 to 3 times, if necessary, in order to obtain a nickel-containing lithium manganese composite oxide having more excellent charge and discharge properties. Further, the heat-treated product obtained can be pulverized, if necessary.
以上、本発明の実施形態について説明したが、本発明はこうした例に何ら限定されるものではなく、本発明の要旨を逸脱しない範囲において種々なる形態で実施し得ることは勿論である。 Although the embodiments of the present invention have been described above, the present invention is not limited to such examples, and it goes without saying that the present invention can be implemented in various forms without departing from the scope of the present invention.
以下、実施例に基づき、本発明の実施形態をより具体的に説明するが、本発明がこれらに限定されるものではない。 Hereinafter, the embodiments of the present invention will be described more specifically based on Examples, but the present invention is not limited thereto.
実施例1
硝酸ニッケル(II)6水和物36.35g、及び塩化マンガン(II)4水和物24.74g（全量0.25モル／バッチ、Ni: Mnモル比1: 1）を500mlの蒸留水に加え完全に溶解させ、金属塩溶液を調製した。別のビーカー（チタン製）に水酸化ナトリウム50gを蒸留水500mlに溶解させた水酸化ナトリウム水溶液を調製し、恒温槽内に設置後、撹拌しながら20℃を保った。この温度管理された水酸化ナトリウム溶液に対して、上記金属塩溶液を3時間程度かけて徐々に滴下することによってNi-Mn沈殿物を形成させた。反応液が完全にアルカリ性（pH11以上）になっていることを確認し沈殿物形成反応を完了させた。作製した沈殿を含むアルカリ溶液を恒温槽から取り出し、混合物を撹拌しつつ酸素を室温で2日間吹き込んで沈殿物を熟成させた。
Example 1
36.35 g of nickel nitrate (II) hexahydrate and 24.74 g of manganese (II) chloride tetrahydrate (total amount 0.25 mol/batch, Ni: Mn molar ratio 1:1) were added to 500 ml of distilled water and completely dissolved. Then, a metal salt solution was prepared. In another beaker (made of titanium), 50 g of sodium hydroxide was dissolved in 500 ml of distilled water to prepare a sodium hydroxide aqueous solution, which was placed in a constant temperature bath and kept at 20° C. with stirring. The metal salt solution was gradually added dropwise to the temperature-controlled sodium hydroxide solution over about 3 hours to form a Ni-Mn precipitate. It was confirmed that the reaction solution was completely alkaline (pH 11 or more), and the precipitate forming reaction was completed. The produced alkaline solution containing the precipitate was taken out from the thermostatic bath, and oxygen was blown into the mixture for 2 days at room temperature while stirring the mixture to age the precipitate.
熟成させた沈殿をビーカーから取り出し、蒸留水で洗浄して過剰のアルカリ成分、塩類等を除去後濾別した。その後Li/(Ni+Mn)比1.00に相当する炭酸リチウム0.125mol(18.47g)を蒸留水200mlに分散させた後、濾別した沈殿とミキサー混合してスラリー状の混合物を作製した。混合物を粉砕して焼成用原料とした。焼成用原料をるつぼに入れ、電気炉内で大気中1時間かけて850℃まで昇温し、その温度で5時間焼成後、炉中で室温付近まで冷却後、炉から取り出し、粉砕して評価用粉末とした。 The aged precipitate was taken out from the beaker, washed with distilled water to remove excess alkali components, salts, etc., and then filtered. After that, 0.125 mol (18.47 g) of lithium carbonate corresponding to a Li/(Ni+Mn) ratio of 1.00 was dispersed in 200 ml of distilled water, and then the filtered precipitate was mixed with a mixer to prepare a slurry-like mixture. The mixture was pulverized into a raw material for firing. Put the raw materials for firing in a crucible, raise the temperature to 850°C over 1 hour in the air in an electric furnace, bake at that temperature for 5 hours, cool to around room temperature in the furnace, remove from the furnace, crush and evaluate. And powder.
X線回折による評価（実施例1）
図２に実施例1で得られた評価用粉末のXRDパターンのフィット状況を、表１にフィットにより得られた結晶学パラメータを示す。図２から実施例1で得られた評価用粉末のXRDパターンは二種の格子定数の異なる六方晶層状岩塩型結晶相にてフィット可能なことが明らかである。表１に記載の結晶学パラメータより、実施例1で得られた評価用粉末は約66モル%の主相と34モル%の副相からなり、さらにこの副相が主相より低いa軸値（2.885Å以下）、低い3b位置遷移金属占有率（g3b値、77.0%以下）、低い組成式あたりの全遷移金属量（gtotal= g3a+g3b値、90.0%以下）を有していることがわかり、本発明のニッケル含有リチウムマンガン複合酸化物が得られたことが明らかである。さらに、実施例1で得られた評価用粉末は2θ= 45°付近の104ピークの半価幅が0.46°と大きく、本発明のニッケル含有リチウムマンガン複合酸化物が得られたことが明らかである。
Evaluation by X-ray diffraction (Example 1)
FIG. 2 shows the fit situation of the XRD pattern of the evaluation powder obtained in Example 1, and Table 1 shows the crystallographic parameters obtained by the fit. It is clear from FIG. 2 that the XRD pattern of the evaluation powder obtained in Example 1 can be fitted with two types of hexagonal layered rock salt type crystal phases having different lattice constants. From the crystallographic parameters listed in Table 1, the evaluation powder obtained in Example 1 consisted of about 66 mol% main phase and 34 mol% subphase, and this subphase had a lower a-axis value than the main phase. (2.885Å or less), low 3b position transition metal occupancy (g 3b value, 77.0% or less), low total transition metal amount per composition formula (g total = g 3a + g 3b value, 90.0% or less) It is clear that the nickel-containing lithium manganese composite oxide of the present invention was obtained. Further, the evaluation powder obtained in Example 1 has a large full width at half maximum of 104 peak near 2θ=45° of 0.46°, and it is clear that the nickel-containing lithium manganese composite oxide of the present invention was obtained. ..
化学分析による評価（実施例1）
実施例1で得られた評価用粉末中のLi量をICP発光分析で、Ni及びMn量を蛍光X線分析により求めた。結果を表１に示す。Li/(Ni+Mn)モル比の値とNi/(Ni+Mn)モル比の値より本発明のニッケル含有リチウムマンガン複合酸化物が得られていることが明らかである。
Evaluation by chemical analysis (Example 1)
The amount of Li in the evaluation powder obtained in Example 1 was determined by ICP emission analysis, and the amounts of Ni and Mn were determined by fluorescent X-ray analysis. The results are shown in Table 1. From the values of Li/(Ni+Mn) molar ratio and Ni/(Ni+Mn) molar ratio, it is clear that the nickel-containing lithium manganese composite oxide of the present invention is obtained.
充放電特性評価（実施例1）
実施例1で得られた評価用粉末20mgを5mgのアセチレンブラック及び0.5mgのポリテトラフルオロエチレン粉末0.5mgと混合して正極合材を作製した。この合材をアルミメッシュに押しつけて正極を作製した。この正極をグローブボックス内にて、有機電解液としてLiPF6を炭酸エチレン及び炭酸ジメチル混合溶媒に溶解させ1Mとしたものを用い、負極として金属リチウム箔を用いてコイン型リチウム二次電池を作製した。本発明のニッケル含有リチウムマンガン複合酸化物の充放電特性を最適化するために段階充電法による電気化学的活性化法を実施した。具体的な活性化法は、以下の通りとした。まず正極を80mAh/gまで電流密度40mA/gで充電させ、その後同じ電流密度で2.0Vまで放電させた。その後40mAh/gずつ充電容量を上げて充放電させ、同様に放電させた。4サイクル目（200mAh/g）まで充電後、2.0Vまで放電し、最後の5サイクル目に4.8Vに達するまで充電させ、その電圧で10mA/gまで保持後、放電させて活性化を完了させた。6サイクル目以降は同じ電流密度で、2.0-4.6Vの電位範囲で29サイクル充放電させてサイクル特性の把握を行った。
Evaluation of charge/discharge characteristics (Example 1)
20 mg of the evaluation powder obtained in Example 1 was mixed with 5 mg of acetylene black and 0.5 mg of polytetrafluoroethylene powder of 0.5 mg to prepare a positive electrode mixture. This composite material was pressed against an aluminum mesh to produce a positive electrode. This positive electrode was used in a glove box to prepare a coin-type lithium secondary battery by using LiPF 6 dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate as an organic electrolyte to 1M and a metal lithium foil as a negative electrode. .. In order to optimize the charge/discharge characteristics of the nickel-containing lithium manganese composite oxide of the present invention, an electrochemical activation method by a step charging method was carried out. The specific activation method was as follows. First, the positive electrode was charged to 80 mAh/g at a current density of 40 mA/g, and then discharged to 2.0 V at the same current density. After that, the charging capacity was increased by 40 mAh/g for charging and discharging, and the discharging was performed in the same manner. After charging to the 4th cycle (200mAh/g), discharge to 2.0V, charge to reach 4.8V at the last 5th cycle, hold at that voltage to 10mA/g, then discharge to complete activation. It was After the 6th cycle, the same current density was used and 29 cycles of charge and discharge were performed in the potential range of 2.0-4.6V to understand the cycle characteristics.
表１及び図３に、実施例1で得られた評価用粉末を用いた充放電特性評価結果を示す。実施例1で得られた評価用粉末は後述する副相を含まない比較例1で得られた評価用粉末に比べて高い初期充放電容量（Q5c及びQ5d）、高い放電電力量（E5d）、高いサイクル後の放電容量（Q34d）、高サイクル特性（100Q34d/Q5d）を示し、本発明のニッケル含有リチウムマンガン複合酸化物の充放電特性上の優位性が明らかである。なお、表１において、Q5cは5サイクル目の充電容量であり初期充電容量に対応する。Q5dは5サイクル目の放電容量であり初期放電容量に対応する。V5dは5サイクル目の放電電圧であり初期放電電圧に対応する。E5dは5サイクル目の放電電力を示す。Q34dは34サイクル目の放電容量であり、100Q34d/Q5dは29サイクルの充放電による容量維持率（サイクル特性）を示す。 Table 1 and FIG. 3 show the results of charge/discharge characteristic evaluation using the evaluation powder obtained in Example 1. The evaluation powder obtained in Example 1 has a higher initial charge/discharge capacity (Q 5c and Q 5d ), higher discharge power (E) than the evaluation powder obtained in Comparative Example 1 containing no subphase described later. 5d ), discharge capacity after high cycle (Q 34d ), and high cycle characteristics (100Q 34d /Q 5d ), the nickel-containing lithium manganese composite oxide of the present invention is clearly superior in charge and discharge characteristics. In Table 1, Q 5c is the charge capacity at the 5th cycle and corresponds to the initial charge capacity. Q 5d is the discharge capacity at the 5th cycle and corresponds to the initial discharge capacity. V 5d is the discharge voltage at the 5th cycle and corresponds to the initial discharge voltage. E 5d indicates the discharge power at the 5th cycle. Q 34d is the discharge capacity at the 34th cycle, and 100Q 34d /Q 5d shows the capacity retention rate (cycle characteristics) by 29 cycles of charging and discharging.
実施例2
最終の焼成温度を950℃5時間大気中焼成にした以外は実施例1と同様に試料作製を行った。
Example 2
A sample was prepared in the same manner as in Example 1 except that the final firing temperature was 950° C. for 5 hours in the air.
X線回折による評価（実施例2）
図４に実施例2で得られた評価用粉末のXRDパターンのフィット状況を、表１にフィットにより得られた結晶学パラメータを示す。図４から実施例2で得られた評価用粉末のXRDパターンは二種の格子定数の異なる六方晶層状岩塩型結晶相にてフィット可能なことが明らかである。表１に記載の結晶学パラメータより、実施例2で得られた評価用粉末は78モル%の主相と22モル%の副相からなり、さらにこの副相が主相より低いa軸値（2.885Å以下）、低い3b位置遷移金属占有率（g3b値、77.0%以下）、低い組成式あたりの全遷移金属量（gtotal= g3a+g3b値、90.0%以下）を有していることがわかり、本発明のニッケル含有リチウムマンガン複合酸化物が得られたことが明らかである。さらに実施例2で得られた評価用粉末は2θ=45°付近の104ピークの半価幅が0.24°と大きく、本発明のニッケル含有リチウムマンガン複合酸化物が得られたことが明らかである。
Evaluation by X-ray diffraction (Example 2)
FIG. 4 shows the fitting condition of the XRD pattern of the evaluation powder obtained in Example 2, and Table 1 shows the crystallographic parameters obtained by the fitting. It is clear from FIG. 4 that the XRD pattern of the evaluation powder obtained in Example 2 can be fitted with two types of hexagonal layered rock salt type crystal phases having different lattice constants. From the crystallographic parameters shown in Table 1, the evaluation powder obtained in Example 2 consisted of 78 mol% of the main phase and 22 mol% of the subphase, and this subphase had a lower a-axis value than the main phase ( 2.885Å or less), low 3b position transition metal occupancy (g 3b value, 77.0% or less), low total transition metal amount per composition formula (g total = g 3a + g 3b value, 90.0% or less) It is clear that the nickel-containing lithium manganese composite oxide of the present invention was obtained. Furthermore, the evaluation powder obtained in Example 2 has a large full width at half maximum of 104 peak around 2θ=45° of 0.24°, and it is clear that the nickel-containing lithium manganese composite oxide of the present invention was obtained.
化学分析による評価（実施例2）
実施例2で得られた評価用粉末中のLi量をICP発光分析で、Ni及びMn量を蛍光X線分析により求めた。結果を表１に示す。Li/(Ni+Mn)モル比の値とNi/(Ni+Mn)モル比の値より本発明のニッケル含有リチウムマンガン複合酸化物が得られていることが明らかである。
Evaluation by chemical analysis (Example 2)
The amount of Li in the evaluation powder obtained in Example 2 was determined by ICP emission analysis, and the amounts of Ni and Mn were determined by fluorescent X-ray analysis. The results are shown in Table 1. From the values of Li/(Ni+Mn) molar ratio and Ni/(Ni+Mn) molar ratio, it is clear that the nickel-containing lithium manganese composite oxide of the present invention is obtained.
充放電特性評価（実施例2）
実施例2で得られた評価用粉末も実施例1と同様に電極合材作製、電気化学的活性化及びサイクル特性評価を行った。表１及び図５に実施例2で得られた評価用粉末の充放電特性評価結果を示す。実施例2で得られた評価用粉末は後述する副相を含まない比較例1で得られた評価用粉末に比べて高い初期充放電容量（Q5c及びQ5d）、高い放電電力量（E5d）、高いサイクル後の放電容量（Q34d）、高サイクル特性（100Q34d/Q5d）を示し、本発明のニッケル含有リチウムマンガン複合酸化物の充放電特性上の優位性が明らかである。
Charge/discharge characteristic evaluation (Example 2)
The evaluation powder obtained in Example 2 was also subjected to electrode mixture preparation, electrochemical activation and cycle characteristic evaluation in the same manner as in Example 1. Table 1 and FIG. 5 show the evaluation results of the charge/discharge characteristics of the evaluation powder obtained in Example 2. The evaluation powder obtained in Example 2 has a higher initial charge/discharge capacity (Q 5c and Q 5d ), higher discharge electric energy (E) than the evaluation powder obtained in Comparative Example 1 containing no subphase described later. 5d ), discharge capacity after high cycle (Q 34d ), and high cycle characteristics (100Q 34d /Q 5d ), the nickel-containing lithium manganese composite oxide of the present invention is clearly superior in charge and discharge characteristics.
比較例1
最終の焼成温度を1000℃5時間大気中焼成にした以外は実施例1と同様に試料作製を行った。
Comparative example 1
A sample was prepared in the same manner as in Example 1 except that the final firing temperature was 1000° C. for 5 hours in the air.
X線回折による評価（比較例1）
図６に比較例1で得られた評価用粉末のXRDパターンのフィット状況を、表１にフィットにより得られた結晶学パラメータを示す。図６から比較例1で得られた評価用粉末のXRDパターンは1種の六方晶層状岩塩型結晶相のみにてフィット可能なことが明らかである。表１に記載の結晶学パラメータより、比較例1で得られた評価用粉末は100モル%の主相のみであり、a軸値（2.885Å以下）、3b位置遷移金属占有率（g3b値、77.0%以下）、組成式あたりの全遷移金属量（gtotal= g3a+g3b値、90.0%以下）いずれも本発明nの範囲から外れ、本発明のニッケル含有リチウムマンガン複合酸化物が得られていないことが明らかである。さらに比較例1で得られた評価用粉末は2θ=45°付近の104ピークの半価幅が0.20°と小さく、本発明のニッケル含有リチウムマンガン複合酸化物が得られていないことが明らかである。
Evaluation by X-ray diffraction (Comparative example 1)
FIG. 6 shows the fit situation of the XRD pattern of the evaluation powder obtained in Comparative Example 1, and Table 1 shows the crystallographic parameters obtained by the fit. From FIG. 6, it is clear that the XRD pattern of the evaluation powder obtained in Comparative Example 1 can be fitted only by one type of hexagonal layered rock salt type crystal phase. Based on the crystallographic parameters shown in Table 1, the evaluation powder obtained in Comparative Example 1 was only 100 mol% of the main phase, a-axis value (2.885 Å or less), 3b position transition metal occupancy (g 3b value). , 77.0% or less), the total amount of transition metal per composition formula (g total = g 3a + g 3b value, 90.0% or less) all outside the range of the present invention n, the nickel-containing lithium manganese composite oxide of the present invention It is clear that it has not been obtained. Furthermore, the evaluation powder obtained in Comparative Example 1 has a small full width at half maximum of 104 peak around 2θ=45° of 0.20°, and it is clear that the nickel-containing lithium manganese composite oxide of the present invention has not been obtained. ..
化学分析による評価（比較例1）
比較例1で得られた評価用粉末中のLi量をICP発光分析で、Ni及びMn量を蛍光X線分析により求めた。結果を表１に示す。Li/(Ni+Mn)モル比の値とNi/(Ni+Mn)モル比の値より本発明のニッケル含有リチウムマンガン複合酸化物との差は若干であることが明らかとなった。
Evaluation by chemical analysis (Comparative example 1)
The amount of Li in the evaluation powder obtained in Comparative Example 1 was determined by ICP emission analysis, and the amounts of Ni and Mn were determined by fluorescent X-ray analysis. The results are shown in Table 1. From the value of the Li/(Ni+Mn) molar ratio and the value of the Ni/(Ni+Mn) molar ratio, it was clarified that the difference between the nickel-containing lithium manganese composite oxide of the present invention was slight.
充放電特性評価（比較例1）
比較例1で得られた評価用粉末も実施例1と同様に電極合材作製、電気化学的活性化及びサイクル特性評価を行った。表１及び図７に比較例1で得られた評価用粉末の充放電特性評価結果を示す。比較例1で得られた評価用粉末は前述した副相を含む実施例1及び2で得られた評価用粉末に比べて低い初期充放電容量（Q5c及びQ5d）、低い放電電力量（E5d）、低いサイクル後の放電容量（Q34d）、低サイクル特性（100Q34d/Q5d）を示し、本発明のニッケル含有リチウムマンガン複合酸化物と異なるために充放電特性上不利となることが明らかである。
Charge/discharge characteristic evaluation (Comparative example 1)
The evaluation powder obtained in Comparative Example 1 was also subjected to electrode mixture preparation, electrochemical activation, and cycle characteristic evaluation in the same manner as in Example 1. Table 1 and FIG. 7 show the evaluation results of the charge/discharge characteristics of the evaluation powder obtained in Comparative Example 1. The evaluation powder obtained in Comparative Example 1 has a lower initial charge/discharge capacity (Q 5c and Q 5d ), and a lower discharge electric energy (compared to the evaluation powders obtained in Examples 1 and 2 containing the subphase described above). E 5d ), discharge capacity after low cycle (Q 34d ), low cycle characteristics (100Q 34d /Q 5d ), which is disadvantageous in charge and discharge characteristics because it is different from the nickel-containing lithium manganese composite oxide of the present invention. Is clear.
以上の実施例及び比較例の結果から、特異な六方晶層状岩塩型結晶相を副相として含むという特徴を有する本発明のニッケル含有リチウムマンガン複合酸化物は、優れた充放電特性を有する正極活物質であることが明らかである。 From the results of the above Examples and Comparative Examples, the nickel-containing lithium manganese composite oxide of the present invention having the characteristic of containing a peculiar hexagonal layered rock salt type crystal phase as a sub-phase has a positive electrode activity having excellent charge/discharge characteristics. Clearly a substance.
Claims (8)
Li1+x(NiyMn1-y)1-xO2 （1）
［式中、x及びyはそれぞれ-0.1<x<0.1、0.4≦y≦0.6を示す。］
で表され、
二種以上の層状岩塩型構造の結晶相を含有し、
そのうち一相の層状岩塩型構造の結晶相（2）は、遷移金属層内格子位置の遷移金属占有率（g3b）が65.0〜77.0%である、ニッケル含有リチウムマンガン複合酸化物。 General formula (1):
Li 1+x (Ni y Mn 1-y ) 1-x O 2 (1)
[In the formula, x and y represent −0.1<x<0.1 and 0.4≦y≦0.6, respectively. ]
Is represented by
Containing a crystalline phase of two or more layered rock salt type structure,
One of the phases, a crystalline phase (2) having a layered rock salt structure, is a nickel-containing lithium manganese composite oxide having a transition metal occupancy (g 3b ) at a lattice position in the transition metal layer of 65.0 to 77.0%.
（1）マンガン化合物及びニッケル化合物を含む混合水溶液から、アルカリ性条件下にて沈殿物を形成する工程、
（2）前記沈殿物に湿式酸化処理を行う工程、及び
（3）リチウム塩共存下酸化性雰囲気下、500〜980℃で熱処理する工程
を備える、製造方法。 A method for producing the nickel-containing lithium manganese composite oxide according to any one of claims 1 to 5,
(1) a step of forming a precipitate under alkaline conditions from a mixed aqueous solution containing a manganese compound and a nickel compound,
(2) A production method comprising a step of subjecting the precipitate to a wet oxidation treatment, and (3) a heat treatment at 500 to 980° C. in an oxidizing atmosphere in the presence of a lithium salt.
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| JP2007257890A (en) * | 2006-03-20 | 2007-10-04 | Nissan Motor Co Ltd | Positive electrode material for nonaqueous lithium ion battery and battery using this |
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| JP2007257890A (en) * | 2006-03-20 | 2007-10-04 | Nissan Motor Co Ltd | Positive electrode material for nonaqueous lithium ion battery and battery using this |
| JP2017527963A (en) * | 2014-08-05 | 2017-09-21 | スリーエム イノベイティブ プロパティズ カンパニー | Cathode composition for lithium ion battery |
| WO2018096999A1 (en) * | 2016-11-28 | 2018-05-31 | 国立研究開発法人産業技術総合研究所 | Lithium-manganese complex oxide and method for producing same |
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