JP2020023424A - Cobalt-manganese-based composite oxide and manufacturing method therefor, and application thereof - Google Patents
Cobalt-manganese-based composite oxide and manufacturing method therefor, and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 138
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 31
- 229910052596 spinel Inorganic materials 0.000 claims description 25
- 239000011029 spinel Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 21
- -1 cobalt salt compound Chemical class 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000012071 phase Substances 0.000 description 26
- 238000005259 measurement Methods 0.000 description 22
- 239000002002 slurry Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 230000033116 oxidation-reduction process Effects 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 229910000733 Li alloy Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride 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
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011899 heat drying method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005550 wet granulation Methods 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、コバルト−マンガン系複合酸化物及びその製造方法、並びにその用途に関するものであり、詳しくは、リチウム−コバルト−マンガン系複合酸化物の前駆体として適したコバルト−マンガン系複合酸化物、そのコバルト−マンガン系複合酸化物を使用するリチウム−コバルト−マンガン系複合酸化物の製造方法、及び、そのリチウム−コバルト−マンガン系複合酸化物を正極として使用するリチウム二次電池に関する。 The present invention relates to a cobalt-manganese-based composite oxide, a method for producing the same, and uses thereof, and more specifically, a cobalt-manganese-based composite oxide suitable as a precursor of a lithium-cobalt-manganese-based composite oxide, The present invention relates to a method for producing a lithium-cobalt-manganese-based composite oxide using the cobalt-manganese-based composite oxide, and a lithium secondary battery using the lithium-cobalt-manganese-based composite oxide as a positive electrode.
リチウム−コバルト−マンガン系複合酸化物は５Ｖ級リチウム二次電池用正極活物質として注目されている。当該リチウム−コバルト−マンガン系複合酸化物（所謂、活物質）の製造方法としては、例えば、リチウム源、コバルト源、及びマンガン源を混合し焼成する固相反応法や、コバルト−マンガン系複合化合物（所謂、前駆体）とリチウム源とを反応させる製造方法が挙げられる。 Lithium-cobalt-manganese-based composite oxides have attracted attention as positive electrode active materials for 5V-class lithium secondary batteries. As a method for producing the lithium-cobalt-manganese composite oxide (so-called active material), for example, a solid phase reaction method in which a lithium source, a cobalt source, and a manganese source are mixed and fired, and a cobalt-manganese composite compound (A so-called precursor) and a production method in which a lithium source is reacted.
Ｆｄ−３ｍの空間群を有する、スピネル型リチウムコバルトマンガン含有複合酸化物が知られている（特許文献１）。前記スピネル型リチウムコバルトマンガン含有複合酸化物は、リチウム源、マンガン源、及びコバルト源を混合し、噴霧熱乾燥法により湿式造粒したものを原料としており、所謂固相反応法によって製造されている。 A spinel-type lithium-cobalt-manganese-containing composite oxide having a space group of Fd-3m is known (Patent Document 1). The spinel-type lithium-cobalt-manganese-containing composite oxide is obtained by mixing a lithium source, a manganese source, and a cobalt source, and performing wet granulation by a spray heat drying method as a raw material, and is manufactured by a so-called solid-phase reaction method. .
特許文献１の固相反応法で得られるスピネル型リチウムコバルトマンガン含有複合酸化物については、コバルトとマンガンが原子レベルで十分に分散されているとは言い難く、均質性に劣るという課題があった。 Regarding the spinel-type lithium cobalt manganese-containing composite oxide obtained by the solid-state reaction method of Patent Document 1, it is difficult to say that cobalt and manganese are sufficiently dispersed at the atomic level, and there is a problem that the homogeneity is poor. .
本発明の目的は、均質性に優れるリチウムコバルトマンガン含有複合酸化物を提供することにあり、そのために、コバルトとマンガンが原子レベルで分散したスピネル型コバルト−マンガン系複合酸化物（前駆体）を提供することにある。 An object of the present invention is to provide a lithium-cobalt-manganese-containing composite oxide having excellent homogeneity. For that purpose, a spinel-type cobalt-manganese-based composite oxide (precursor) in which cobalt and manganese are dispersed at an atomic level is provided. To provide.
本発明者はコバルト−マンガン系複合酸化物について鋭意検討した結果、従来にない、Ｃｏ：Ｍｎ組成（モル比）が１：１付近のスピネル型複合酸化物を見出し、本発明を完成するに至った。すなわち、本発明は、化学組成式がＣｏ（１．５＋ｘ）Ｍｎ（１．５−ｘ）Ｏ４（但し、−０．１５≦ｘ≦０．１５である）で表され、結晶構造が立方晶スピネル型構造であることを特徴とするコバルト−マンガン系複合酸化物、その製造方法、並びにその用途に関する。 As a result of intensive studies on the cobalt-manganese-based composite oxide, the present inventors have found a spinel-type composite oxide having an unconventional Co: Mn composition (molar ratio) of about 1: 1 and completed the present invention. Was. That is, the present invention is the chemical composition formula Co (1.5 + x) Mn ( 1.5-x) O 4 ( where a is -0.15 ≦ x ≦ 0.15) is represented by the crystal structure is cubic The present invention relates to a cobalt-manganese-based composite oxide having a crystalline spinel structure, a method for producing the same, and uses thereof.
本発明のコバルト−マンガン系複合酸化物（前駆体）は、単一結晶相に極めて近いため、リチウム源と反応させることによって、金属元素の均質性に優れるスピネル型リチウムコバルトマンガン含有複合酸化物（活物質）を提供することができる。 Since the cobalt-manganese-based composite oxide (precursor) of the present invention is very close to a single crystal phase, by reacting with a lithium source, a spinel-type lithium-cobalt-manganese-containing composite oxide having excellent metal element homogeneity ( Active material) can be provided.
また、本発明のコバルト−マンガン系複合酸化物は、保存安定性に優れるという効果を奏する。 Further, the cobalt-manganese-based composite oxide of the present invention has an effect of being excellent in storage stability.
また、本発明のコバルト−マンガン系複合酸化物を前駆体としたリチウム−コバルト−マンガン系複合酸化物は、従来公知の固相反応法リチウム−コバルト−マンガン系複合酸化物に比べて、リチウム二次電池を高性能化することができるという効果を奏する。 In addition, the lithium-cobalt-manganese-based composite oxide using the cobalt-manganese-based composite oxide of the present invention as a precursor is more lithium-cobalt-manganese-based composite oxide than a conventionally known solid-state reaction method lithium-cobalt-manganese-based composite oxide. There is an effect that the performance of the secondary battery can be improved.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のコバルト−マンガン系複合酸化物は、化学組成式がＣｏ（１．５＋ｘ）Ｍｎ（１．５−ｘ）Ｏ４（但し、−０．１５≦ｘ≦０．１５である）で表される。 Table manganese-based composite oxide, the chemical composition formula Co (1.5 + x) Mn ( 1.5-x) O 4 ( provided that -0.15 ≦ x ≦ 0.15) - cobalt present invention Is done.
上記のｘについては、−０．１５≦ｘ≦０．１５であるが、ｘがこの範囲内であれば、酸化還元に関与するコバルトの含有量が担保でき、５Ｖ付近（Ｌｉ金属負極基準）の電池容量をより多く利用できる。なお、当該ｘについては、−０．１０≦ｘ≦０．１０であることが好ましく、−０．０５≦ｘ≦０．０５であることがさらに好ましい。 X is -0.15 ≦ x ≦ 0.15, but if x is within this range, the content of cobalt involved in oxidation-reduction can be ensured, and around 5 V (based on a Li metal negative electrode). More battery capacity available. Note that x is preferably -0.10≤x≤0.10, and more preferably -0.05≤x≤0.05.
本発明のコバルト−マンガン系複合酸化物は、結晶構造が立方晶スピネル型構造である。立方晶スピネル型であることにより、ＣｏおよびＭｎの元素分布が均一化され、Ｃｏ−Ｍｎ規則配列が実現しやすい利点がある。また、原料および最終生成物であるリチウム−コバルト−マンガン系複合酸化物の両方がスピネル型構造であることで、原料とリチウム化合物との反応が円滑に進行しやすいという利点がある。ここに、立方晶スピネル型とは、結晶格子が立方晶に分類され、結晶構造はスピネル型であるものをいい、空間群がＦｄ−３ｍであることが好ましい。また、立方晶スピネル型酸化物の含有率が高く主相となるため、格子定数ａが８．１５〜８．３５Åであることが好ましく、８．２０〜８．３０Åがより好ましく、８．２２〜８．３０Åがさらに好ましく、８．２５〜８．３０Åが特に好ましい。格子定数ａが８．２５〜８．３０Åの場合、極めて単一結晶相に近い結晶相が得られる。結晶構造が立方晶スピネル型構造とは、立方晶スピネル型構造の単一結晶相だけではなく、立方晶スピネル型構造が主相となっており、オキシ水酸化物、ハイドロタルサイト型水酸化物のいずれかまたは両方が微量生成して副相になっていてもよい。 The cobalt-manganese composite oxide of the present invention has a cubic spinel structure. The cubic spinel type has the advantage that the element distributions of Co and Mn are made uniform, and Co-Mn regular arrangement is easily realized. In addition, since both the raw material and the lithium-cobalt-manganese-based composite oxide as the final product have a spinel structure, there is an advantage that the reaction between the raw material and the lithium compound easily proceeds smoothly. Here, the cubic spinel type means that the crystal lattice is classified as cubic and the crystal structure is a spinel type, and the space group is preferably Fd-3m. Further, since the content of the cubic spinel-type oxide is high and the main phase becomes a main phase, the lattice constant a is preferably from 8.15 to 8.35 °, more preferably from 8.20 to 8.30 °, and 8.22. To 8.30 ° is more preferable, and 8.25 to 8.30 ° is particularly preferable. When the lattice constant a is 8.25 to 8.30 °, a crystal phase very close to a single crystal phase is obtained. The cubic spinel structure is not only a cubic spinel structure but also a cubic spinel structure. Either or both of them may be formed in a trace amount to form a subphase.
本発明のコバルト−マンガン系複合酸化物は、Ｎａ含有量が３０００ｐｐｍ以下であることが好ましい。Ｎａ含有量が３０００ｐｐｍ以下の場合、当該コバルト−マンガン系複合酸化物を用いて得られたリチウム−コバルト−マンガン系複合酸化物においてリチウムの移動が阻害されず、放電容量が増加する傾向にある。当該Ｎａ含有量については、放電容量に優れる点で、２０００ｐｐｍ以下がより好ましく、１７００ｐｐｍ以下がより一層好ましく、１５００ｐｐｍ以下がさらに好ましく、１２００ｐｐｍ以下が特に好ましく、１０００ｐｐｍ以下が最も好ましい。 The cobalt-manganese-based composite oxide of the present invention preferably has a Na content of 3000 ppm or less. When the Na content is 3000 ppm or less, the lithium-cobalt-manganese composite oxide obtained by using the cobalt-manganese composite oxide does not hinder the movement of lithium and tends to increase the discharge capacity. The Na content is preferably 2,000 ppm or less, more preferably 1,700 ppm or less, still more preferably 1,500 ppm or less, particularly preferably 1,200 ppm or less, most preferably 1,000 ppm or less, from the viewpoint of excellent discharge capacity.
本発明のコバルト−マンガン系複合酸化物は、ＳＯ４含有量が１重量％以下であることが好ましい。ＳＯ４含有量が１重量％以下の場合、当該コバルト−マンガン系複合酸化物を用いてリチウム−コバルト−マンガン系複合酸化物を製造したときに、Ｌｉ金属と化合物を形成してＬｉ２ＳＯ４などが局部的に生成されるのを抑え、電池容量が増加する傾向にある。そのため、当該ＳＯ４含有量については、０．６重量％以下がより好ましく、０．３重量％以下がさらに好ましい。 The cobalt-manganese-based composite oxide of the present invention preferably has an SO 4 content of 1% by weight or less. When the content of SO 4 is 1% by weight or less, when a lithium-cobalt-manganese composite oxide is manufactured using the cobalt-manganese composite oxide, a compound is formed with Li metal to form Li 2 SO 4. And the like are suppressed from being generated locally, and the battery capacity tends to increase. Therefore, the SO 4 content is more preferably 0.6% by weight or less, and further preferably 0.3% by weight or less.
本発明のコバルト−マンガン系複合酸化物の平均粒子径は、特に限定するものではないが、例えば、電極を形成しやすいという点で、１〜２０μｍが好ましく、２〜２０μｍがより好ましく、２〜１５μｍがさらに好ましい。なお、当該平均粒子径とは、一次粒子が凝集した二次粒子の平均粒子径のことを表し、いわゆる凝集粒子径を表す。 The average particle diameter of the cobalt-manganese-based composite oxide of the present invention is not particularly limited. For example, from the viewpoint of easily forming an electrode, 1 to 20 μm is preferable, 2 to 20 μm is more preferable, and 2 to 20 μm is more preferable. 15 μm is more preferred. In addition, the said average particle diameter represents the average particle diameter of the secondary particle which the primary particle aggregated, and represents the so-called aggregated particle diameter.
本発明のコバルト−マンガン系複合酸化物の粒子径分布は、特に限定するものではなく、例えば、単分散の粒子径分布、二峰性の粒子径分布等が挙げられる。単分散、すなわち、モノモーダルな分布を有する粒子径分布である場合には、正極とした際にも粒子径が均一であるため、その充放電反応もより均一なものとなる。 The particle size distribution of the cobalt-manganese composite oxide of the present invention is not particularly limited, and examples thereof include a monodisperse particle size distribution and a bimodal particle size distribution. In the case of monodispersion, that is, a particle size distribution having a monomodal distribution, the charge / discharge reaction becomes more uniform since the particle size is uniform even when the cathode is used.
本発明のコバルト−マンガン系複合酸化物のＢＥＴ比表面積は、特に限定するものではないが、高い充填性が得られやすいという点で、１００ｍ２／ｇ以下であることが好ましく、７５ｍ２／ｇ以下であることがより好ましく、５０ｍ２／ｇ以下であることがさらに好ましく、２５ｍ２／ｇ以下であることが特に好ましく、１５ｍ２／ｇ以下であることが最も好ましい。一般的には、充填性とＢＥＴ比表面積とは相関関係があるため、低比表面積の方が高い充填性の粉末が得られやすい。 The BET specific surface area of the cobalt-manganese-based composite oxide of the present invention is not particularly limited, but is preferably 100 m 2 / g or less, and is preferably 75 m 2 / g in that high filling properties are easily obtained. Is more preferably 50 m 2 / g or less, particularly preferably 25 m 2 / g or less, and most preferably 15 m 2 / g or less. Generally, since there is a correlation between the filling property and the BET specific surface area, a powder having a high specific filling property is easily obtained with a low specific surface area.
次に、本発明のコバルト−マンガン系複合酸化物の製造方法について説明する。 Next, a method for producing the cobalt-manganese composite oxide of the present invention will be described.
本発明のコバルト−マンガン系複合酸化物は、ｐＨ８．０〜１２．０の条件下、コバルト塩化合物とマンガン塩化合物を含む水溶液と酸化剤を、酸化還元電位−０．２〜０．３Ｖで混合することによって製造することができ、当該操作によって混合水溶液中に目的とするコバルト−マンガン系複合酸化物を析出させることができる。 The cobalt-manganese-based composite oxide of the present invention is obtained by converting an aqueous solution containing a cobalt salt compound and a manganese salt compound and an oxidizing agent under a condition of pH 8.0 to 12.0 at an oxidation-reduction potential of -0.2 to 0.3 V. It can be manufactured by mixing, and the desired cobalt-manganese-based composite oxide can be precipitated in the mixed aqueous solution by the operation.
コバルト塩化合物としては、特に限定するものではないが、例えば、コバルト硫酸塩、コバルト塩化物、コバルト硝酸塩、コバルト酢酸塩などを例示することができる。コバルト塩化合物を含む水溶液としては、特に限定するものではないが、例えば、コバルト硫酸塩、コバルト塩化物、コバルト硝酸塩、コバルト酢酸塩などを溶解させた水溶液や、硫酸、塩酸、硝酸などの無機酸、酢酸などの酸にコバルトを溶解した水溶液等を挙げることができる。当該コバルト塩化合物としては、硫酸コバルトが好ましい。 Although it does not specifically limit as a cobalt salt compound, For example, a cobalt sulfate, a cobalt chloride, a cobalt nitrate, a cobalt acetate, etc. can be illustrated. The aqueous solution containing the cobalt salt compound is not particularly limited. For example, an aqueous solution in which cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt acetate, or the like is dissolved, or an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid is used. And an aqueous solution in which cobalt is dissolved in an acid such as acetic acid. As the cobalt salt compound, cobalt sulfate is preferable.
マンガン塩化合物としては、特に限定するものではないが、例えば、マンガン硫酸塩、マンガン塩化物、マンガン硝酸塩、マンガン酢酸塩などを例示することができる。マンガン塩化合物を含む水溶液としては、特に限定するものではないが、例えば、マンガン硫酸塩、マンガン塩化物、マンガン硝酸塩、マンガン酢酸塩などを溶解させた水溶液や、硫酸、塩酸、硝酸などの無機酸、酢酸などの酸にマンガンを溶解した水溶液等を挙げることができる。当該マンガン塩化合物としては、硫酸マンガンが好ましい。 Although it does not specifically limit as a manganese salt compound, For example, manganese sulfate, manganese chloride, manganese nitrate, manganese acetate, etc. can be illustrated. The aqueous solution containing a manganese salt compound is not particularly limited, and examples thereof include an aqueous solution in which manganese sulfate, manganese chloride, manganese nitrate, and manganese acetate are dissolved, and inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. And an aqueous solution in which manganese is dissolved in an acid such as acetic acid. As the manganese salt compound, manganese sulfate is preferable.
また、本発明の製造方法において、コバルトとマンガンの割合は、目的とするコバルト−マンガン系複合酸化物のコバルト：マンガンの割合となるようにすることが好ましい。したがって、コバルト、マンガンの割合は、モル比でＣｏ：Ｍｎ＝１．５０＋ｘ：１．５０−ｘ（但し、−０．１５≦ｘ≦０．１５である）であることが好ましい。 Further, in the production method of the present invention, the ratio of cobalt and manganese is preferably set to be the ratio of cobalt: manganese of the target cobalt-manganese-based composite oxide. Therefore, the ratio of cobalt and manganese is preferably Co: Mn = 1.50 + x: 1.50-x (provided that -0.15 ≦ x ≦ 0.15) in molar ratio.
金属塩水溶液中のコバルト、マンガンの合計濃度（金属濃度）は任意であるが、生産性に優れるという点で、１．０ｍｏｌ／Ｌ以上が好ましく、２．０ｍｏｌ／Ｌ以上がより好ましい。 The total concentration (metal concentration) of cobalt and manganese in the aqueous metal salt solution is arbitrary, but is preferably 1.0 mol / L or more, more preferably 2.0 mol / L or more, from the viewpoint of excellent productivity.
ｐＨ８．０〜１２．０の反応条件を維持するためには、酸や塩基を適宜添加混合することが好ましい。当該酸については、特に限定するものではないが、例えば、硫酸、塩酸、硝酸、又は酢酸などを挙げることができる。当該塩基については、特に限定するものではないが、例えば、苛性ソーダ、苛性カリ、水酸化リチウム、水酸化カルシウム、水酸化バリウム、炭酸ソーダ、重炭酸ソーダ等を挙げることができる。 In order to maintain the reaction conditions of pH 8.0 to 12.0, it is preferable to appropriately add and mix an acid or a base. The acid is not particularly limited, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, and acetic acid. The base is not particularly limited, and examples thereof include caustic soda, caustic potash, lithium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, and sodium bicarbonate.
当該酸や塩基を添加する際、酸や塩基については、直接添加してもよいし、水溶液として添加してもよい。水溶液として添加する場合、その濃度については、特に限定するものではないが、例えば、１ｍｏｌ／Ｌ以上を例示することができる。 When the acid or base is added, the acid or base may be added directly or as an aqueous solution. When added as an aqueous solution, the concentration thereof is not particularly limited, but for example, 1 mol / L or more can be exemplified.
本発明において、ｐＨ８．０〜１２．０の反応条件を維持するためには、苛性ソーダ水溶液を添加することが好ましく、苛性ソーダ水溶液としては、例えば、固形状水酸化ナトリウムを水溶させたものや食塩電解から生成した水酸化ナトリウム水溶液を濃度調製したもの等を用いることができる。 In the present invention, in order to maintain the reaction conditions of pH 8.0 to 12.0, it is preferable to add an aqueous solution of caustic soda. As the aqueous solution of caustic soda, for example, one obtained by dissolving solid sodium hydroxide in water or salt electrolysis The concentration of an aqueous solution of sodium hydroxide generated from the above can be used.
本発明の製造方法において、ｐＨを制御するために酸や塩基を添加混合する方法としては、特に限定するものではなく、例えば、連続的に行ってもよく、断続的に行ってもよい。 In the production method of the present invention, the method of adding and mixing an acid or a base for controlling the pH is not particularly limited, and may be, for example, continuous or intermittent.
酸化剤は、特に限定するものではないが、例えば、有酸素ガス又は過酸化水素水を挙げることができる。有酸素ガスとしては、特に限定するものではないが、例えば、空気、酸素等を例示することができる。経済上、空気が最も好ましい。空気や酸素などのガスはバブラーなどを用いてバブリングさせることで添加する。一方、過酸化水素水は金属塩水溶液や苛性ソーダ水溶液と同様に混合することができる。過酸化水素水の濃度としては、３〜３０重量％を例示することができる。 The oxidizing agent is not particularly limited, and examples thereof include an aerobic gas and a hydrogen peroxide solution. Although it does not specifically limit as an aerobic gas, For example, air, oxygen, etc. can be illustrated. Air is most preferred for economy. Gases such as air and oxygen are added by bubbling using a bubbler or the like. On the other hand, the aqueous hydrogen peroxide can be mixed similarly to the aqueous metal salt solution or the aqueous caustic soda solution. Examples of the concentration of the hydrogen peroxide solution include 3 to 30% by weight.
本発明の製造方法については、ｐＨ８．０〜１２．０の条件で行うものである。ｐＨ８．０未満であると、コバルトとマンガンの溶解度の差が顕著になることで、目的のコバルトとマンガンの組成比ずれが起き、ｐＨ１２．０を超えると、結晶性が低下し、非晶質化する。立方晶スピネル型酸化物の生産比率を高められるという点で、ｐＨ８．０〜１１．０であることが好ましく、ｐＨ８．０〜９．５であることがより好ましい。さらに、高い製造効率での製造が可能になるという点で、ｐＨ８．２５〜９．２５であることが特に好ましい。 The production method of the present invention is carried out under the condition of pH 8.0 to 12.0. If the pH is less than 8.0, the difference in solubility between cobalt and manganese becomes remarkable, causing a deviation in the composition ratio of the target cobalt and manganese. Become From the viewpoint that the production ratio of the cubic spinel-type oxide can be increased, the pH is preferably 8.0 to 11.0, and more preferably 8.0 to 9.5. Further, the pH is particularly preferably from 8.25 to 9.25 in that the production can be performed with high production efficiency.
本発明の製造方法については、コバルト塩化合物とマンガン塩化合物を含む水溶液と酸化剤を、酸化還元電位−０．２〜０．３Ｖで混合するものである。酸化還元電位も生成される結晶構造に影響し、酸化還元電位が０．３Ｖを超えると、マンガンの析出電位から外れ、コバルトとマンガンの組成比ずれが引き起こされる。一方、酸化還元電位が−０．２Ｖ未満であると、結晶性が低下し非晶質化する。単一結晶相により近づけるためには−０．１〜０．２Ｖの範囲が好ましい。酸化還元電位は酸化剤の供給量により制御可能である。 In the production method of the present invention, an aqueous solution containing a cobalt salt compound and a manganese salt compound and an oxidizing agent are mixed at an oxidation-reduction potential of -0.2 to 0.3 V. The oxidation-reduction potential also affects the crystal structure to be produced. If the oxidation-reduction potential exceeds 0.3 V, the oxidation-reduction potential deviates from the manganese deposition potential, causing a shift in the composition ratio between cobalt and manganese. On the other hand, if the oxidation-reduction potential is less than -0.2 V, the crystallinity is reduced and the film becomes amorphous. In order to make it closer to a single crystal phase, the range of -0.1 to 0.2 V is preferable. The oxidation-reduction potential can be controlled by the supply amount of the oxidizing agent.
コバルト塩化合物とマンガン塩化合物を含む水溶液に酸化剤を添加するときの温度は、特に限定するものではないが、通常、４０℃以上であることが好ましい。なお、金属塩水溶液の酸化反応が進みやすくなり、コバルト−マンガン系複合酸化物がより析出しやすいという点で、５０℃以上がより好ましく、６０℃以上がさらに好ましく、６０〜８０℃が特に好ましい。 The temperature at which the oxidizing agent is added to the aqueous solution containing the cobalt salt compound and the manganese salt compound is not particularly limited, but is usually preferably 40 ° C. or higher. In addition, 50 degreeC or more is more preferable, 60 degreeC or more is more preferable, and 60-80 degreeC is especially preferable that the oxidation reaction of a metal salt aqueous solution progresses easily and a cobalt-manganese-type composite oxide is easy to precipitate. .
本発明のコバルト−マンガン系複合酸化物の製造方法については、特に雰囲気制御は必要なく、通常の大気雰囲気下で行うことが可能である。 The method for producing the cobalt-manganese-based composite oxide of the present invention does not require any particular atmosphere control, and can be carried out under a normal atmosphere.
本発明のコバルト−マンガン系複合酸化物の製造方法については、バッチ式、連続式のどちらでも可能である。バッチ式の場合、混合時間は任意である。例えば、３〜４８時間が挙げられ、さらには６〜２４時間を挙げることができる。一方、連続式の場合、コバルト−マンガン系複合酸化物粒子が反応容器内に滞在する平均滞在時間を１〜３０時間にするのが好ましく、３〜２０時間がより好ましい。 The method for producing the cobalt-manganese composite oxide of the present invention can be either a batch type or a continuous type. In the case of a batch type, the mixing time is optional. For example, it may be 3 to 48 hours, and more preferably 6 to 24 hours. On the other hand, in the case of the continuous type, the average stay time of the cobalt-manganese composite oxide particles staying in the reaction vessel is preferably set to 1 to 30 hours, more preferably 3 to 20 hours.
本発明のコバルト−マンガン系複合酸化物の製造方法によって析出したコバルト−マンガン系複合酸化物については、濾過などの操作によって単離することができ、さらに、取り扱い上、さらに洗浄を行って、乾燥することが好ましい。 The cobalt-manganese-based composite oxide precipitated by the method for producing a cobalt-manganese-based composite oxide of the present invention can be isolated by an operation such as filtration, and further washed on handling and dried. Is preferred.
洗浄によって、コバルト−マンガン系複合酸化物に付着、吸着した不純物を除去することができる。洗浄方法としては、特に限定するものではないが、例えば、水（例えば、純水、水道水、河川水等）にコバルト−マンガン系複合酸化物を添加し、不純物を水に溶解させる方法が例示できる。 By the washing, impurities adhering to and adsorbing to the cobalt-manganese composite oxide can be removed. The washing method is not particularly limited. For example, a method of adding a cobalt-manganese-based composite oxide to water (for example, pure water, tap water, river water, etc.) and dissolving impurities in water is exemplified. it can.
乾燥によって、コバルト−マンガン系複合酸化物の水分を除去することができる。乾燥方法としては、特に限定するものではないが、例えば、コバルト−マンガン系複合酸化物を１１０〜１５０℃で２〜１５時間で加熱乾燥する等が挙げられる。 By drying, moisture of the cobalt-manganese composite oxide can be removed. The drying method is not particularly limited, and examples thereof include heating and drying the cobalt-manganese composite oxide at 110 to 150 ° C for 2 to 15 hours.
本発明の製造方法では、洗浄し、乾燥した後に、粉砕を行ってもよい。 In the production method of the present invention, pulverization may be performed after washing and drying.
粉砕では、用途に適した平均粒子径の粉末とする。所望の平均粒子径となれば粉砕条件は任意であり、例えば、湿式粉砕、乾式粉砕等の方法で粉砕することが例示できる。 In the pulverization, a powder having an average particle diameter suitable for use is obtained. The pulverization conditions are arbitrary as long as the desired average particle diameter is obtained. For example, pulverization by a method such as wet pulverization or dry pulverization can be exemplified.
本発明のコバルト−マンガン系複合酸化物は、リチウム−コバルト−マンガン系複合酸化物の製造に使用することができる。 The cobalt-manganese composite oxide of the present invention can be used for producing a lithium-cobalt-manganese composite oxide.
本発明のコバルト−マンガン系複合酸化物を原料として、リチウム−コバルト−マンガン系複合酸化物を製造する場合、その製造方法は、コバルト−マンガン系複合酸化物とリチウム化合物とを混合する混合工程と、焼成工程と、アニール工程を有するものである。 When the lithium-cobalt-manganese-based composite oxide is produced using the cobalt-manganese-based composite oxide of the present invention as a raw material, the production method includes a mixing step of mixing the cobalt-manganese-based composite oxide with a lithium compound. , A firing step, and an annealing step.
混合工程において、リチウム化合物は任意のものを用いることができる。リチウム化合物として、例えば、水酸化リチウム、酸化リチウム、炭酸リチウム、ヨウ化リチウム、硝酸リチウム、シュウ酸リチウム及びアルキルリチウムの群から選ばれる１種以上が例示できる。好ましいリチウム化合物として、水酸化リチウム、酸化リチウム及び炭酸リチウムの群から選ばれるいずれか１種以上が例示できる。 In the mixing step, any lithium compound can be used. Examples of the lithium compound include one or more selected from the group consisting of lithium hydroxide, lithium oxide, lithium carbonate, lithium iodide, lithium nitrate, lithium oxalate, and alkyllithium. Preferred lithium compounds include one or more selected from the group consisting of lithium hydroxide, lithium oxide and lithium carbonate.
焼成工程では、混合工程で得られた混合物を焼成することによってリチウム−コバルト−マンガン系複合酸化物を製造することができる。焼成は、特に限定するものではないが、通常、５００〜１０００℃の温度範囲で行うことができる。当該焼成については、空気中、酸素中など各種の雰囲気で行うことができる。 In the firing step, a lithium-cobalt-manganese-based composite oxide can be produced by firing the mixture obtained in the mixing step. Although calcination is not particularly limited, it can be usually performed in a temperature range of 500 to 1000 ° C. The firing can be performed in various atmospheres such as in air or oxygen.
アニール工程では、５００〜８００℃の温度範囲が好ましく、６００〜７５０℃の温度範囲がより好ましく、例えば、大気や酸素の雰囲気下に０．５〜３００時間置くことで、酸素を取り込みやすくすることが好ましい。アニール工程を行わない場合、酸素の欠損量が大きくなり、充放電容量が低下する。 In the annealing step, a temperature range of 500 to 800 ° C. is preferable, and a temperature range of 600 to 750 ° C. is more preferable. For example, by placing in an atmosphere of air or oxygen for 0.5 to 300 hours, oxygen can be easily taken in. Is preferred. If the annealing step is not performed, the amount of oxygen deficiency increases, and the charge / discharge capacity decreases.
このように得られたリチウム−コバルト−マンガン系複合酸化物については、リチウム二次電池の正極活物質として用いられる。 The lithium-cobalt-manganese-based composite oxide thus obtained is used as a positive electrode active material of a lithium secondary battery.
本発明のリチウム二次電池に用いる負極活物質としては、金属リチウムおよびリチウムまたはリチウムイオンを吸蔵放出可能な物質を用いることができる。例えば、金属リチウム、リチウム／アルミニウム合金、リチウム／スズ合金、リチウム／鉛合金および電気化学的にリチウムイオンを挿入・脱離することができる炭素材料が例示され、電気化学的にリチウムイオンを挿入・脱離することができる炭素材料が安全性および電池の特性の面から特に好適である。 As the negative electrode active material used for the lithium secondary battery of the present invention, metal lithium and a substance capable of inserting and extracting lithium or lithium ions can be used. For example, metallic lithium, lithium / aluminum alloy, lithium / tin alloy, lithium / lead alloy, and a carbon material capable of electrochemically inserting / desorbing lithium ions are exemplified. A carbon material that can be desorbed is particularly suitable in terms of safety and battery characteristics.
本発明のリチウム二次電池で用いる電解質としても特に制限はなく、例えば、カーボネート類、スルホラン類、ラクトン類、エーテル顆等の有機溶媒中にリチウム塩を溶解したものや、リチウムイオン導電性の固体電解質を用いることができる。 The electrolyte used in the lithium secondary battery of the present invention is not particularly limited, for example, carbonates, sulfolane, lactones, those obtained by dissolving a lithium salt in an organic solvent such as ether, or a lithium ion conductive solid An electrolyte can be used.
本発明のリチウム二次電池で用いるセパレーターとしては、特に制限はないが、例えば、ポリエチレン製、ポリプロピレン製の微細多孔膜等を用いることができる。 The separator used in the lithium secondary battery of the present invention is not particularly limited. For example, a microporous film made of polyethylene or polypropylene can be used.
以上のようなリチウム二次電池の構成の一例として、例えば、導電剤との混合物をペレット状に成型した後、１００〜２００℃で減圧乾燥して得られる成形物を電池用正極とし、金属リチウム箔からなる負極、およびエチレンカーボネートとジエチルカーボネートとの混合溶媒に六フッ化リン酸リチウムを溶解した電解液を用いたもの等が挙げられる。 As an example of the configuration of the lithium secondary battery as described above, for example, a mixture obtained by molding a mixture with a conductive agent into a pellet, and then dried under reduced pressure at 100 to 200 ° C. is used as a battery positive electrode to form a metallic lithium. Examples thereof include a negative electrode made of a foil, and an electrolytic solution in which lithium hexafluorophosphate is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate.
以下、本発明を実施例により更に詳細に説明するが、これらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.
＜粉末Ｘ線回折測定＞
Ｘ線回折装置（商品名：Ｕｌｔｉｍａ４、リガク製）を使用し、得られた試料の粉末Ｘ線回折測定を行った。線源にはＣｕＫα線（λ＝１．５４０５Å）を用い、測定モードはステップスキャン、スキャン条件はサンプリング幅２θ＝０．０４°、計測時間は４秒、測定範囲は２θとして１０°から９０°の範囲で測定した。
<Powder X-ray diffraction measurement>
Using an X-ray diffractometer (trade name: Ultima4, manufactured by Rigaku Corporation), the obtained sample was subjected to powder X-ray diffraction measurement. CuKα ray (λ = 1.5405 °) was used as the radiation source, the measurement mode was step scan, the scan conditions were a sampling width 2θ = 0.04 °, the measurement time was 4 seconds, and the measurement range was 10 ° to 90 ° as 2θ. It measured in the range of.
＜結晶構造の解析と格子定数の測定＞
上記の条件のＸＲＤ測定で得られたＸＲＤパターンにおいて、立方晶スピネル型結晶相の構造精密化をＲｉｅｔｖｅｌｄ法で行った。Ｘ線回折装置に付属の解析ソフトウェアＰＤＸＬ−２を用いてパターンフィッティングすることにより、格子定数ａを求めた。副生相であるオキシ水酸化物型構造は２θ＝１９．２°±０．５°及び２θ＝６６．０°±０．５°、ハイドロタルサイト型酸化物構造については、２θ＝１１．７°±１．０°の立方晶スピネル型構造では帰属不可能な回折ピークを確認することにより、それらの生成を確認した。また、オキシ水酸化物型構造は２θ＝１９．２°±０．５°にもっとも強く回折ピークが現れるが、立方晶スピネル型構造の結晶相がもつ２θ＝１８．５°±０．５°の回折ピークと重複した場合、一本の合成ピークとして現れることがある。この場合、他の回折ピークとの強度比を比較することにより、オキシ水酸化物型構造の有無を確認した。
<Analysis of crystal structure and measurement of lattice constant>
In the XRD pattern obtained by the XRD measurement under the above conditions, the structure of the cubic spinel-type crystal phase was refined by the Rietveld method. The lattice constant a was determined by performing pattern fitting using analysis software PDXL-2 attached to the X-ray diffraction apparatus. 2θ = 19.2 ° ± 0.5 ° and 2θ = 66.0 ° ± 0.5 ° for the oxyhydroxide type structure as a by-product phase, and 2θ = 11.1 for the hydrotalcite type oxide structure. The generation thereof was confirmed by confirming diffraction peaks that could not be assigned in the cubic spinel structure at 7 ° ± 1.0 °. In the oxyhydroxide type structure, a diffraction peak appears most strongly at 2θ = 19.2 ° ± 0.5 °, but the 2θ = 18.5 ° ± 0.5 ° of the cubic spinel type crystal phase has. When it overlaps with the diffraction peak of, it may appear as one synthetic peak. In this case, the presence or absence of an oxyhydroxide type structure was confirmed by comparing the intensity ratio with other diffraction peaks.
＜化学組成の測定＞
得られた試料の組成分析は誘導結合プラズマ発光分析法（ＩＣＰ法）により行った。すなわち、試料粉末と過酸化水素水と塩酸水溶液とを加熱酸溶解することで、測定溶液を調製した。一般的な誘導結合プラズマ発光分析装置（商品名：ＯＰＴＩＭＡ３０００ＤＶ、ＰＥＲＫＩＮ ＥＬＭＥＲ製）を用い、得られた測定溶液を測定することで、得られた試料の化学組成を分析した。
<Measurement of chemical composition>
The composition of the obtained sample was analyzed by inductively coupled plasma emission spectrometry (ICP method). That is, a measurement solution was prepared by dissolving a sample powder, a hydrogen peroxide solution, and a hydrochloric acid aqueous solution in a heated acid. The chemical composition of the obtained sample was analyzed by measuring the obtained measurement solution using a general inductively coupled plasma emission analyzer (trade name: OPTIMA3000DV, manufactured by PERKIN ELMER).
＜平均粒子径の測定＞
得られた試料の平均粒子径は、レーザー回折式粒度分布測定装置（商品名：マイクロトラックＭＴ３３００ＥＸＩＩ、マイクロトラックベル製）を使用してＨＲＡモードで測定した。
<Measurement of average particle size>
The average particle diameter of the obtained sample was measured in an HRA mode using a laser diffraction particle size distribution analyzer (trade name: Microtrac MT3300EXII, manufactured by Microtrac Bell).
＜比表面積の測定＞
流動式比表面積自動測定装置（商品名：フローソーブ３−２３０５、Ｍｉｃｒｏｍｅｔｒｉｃｓ社製）を用い、得られた複合酸化物１．０ｇを窒素気流中１５０℃、１時間前処理した後、ＢＥＴ１点法にて吸脱着面積を測定した後、重量で除することで比表面積（ｍ２／ｇ）を求めた。
<Measurement of specific surface area>
Using a fluid type specific surface area automatic measuring device (trade name: Flowsorb 3-2305, manufactured by Micrometrics), 1.0 g of the obtained composite oxide was pretreated in a nitrogen stream at 150 ° C. for 1 hour, and then subjected to the BET one-point method. The specific surface area (m 2 / g) was obtained by measuring the adsorption / desorption area by dividing by weight.
＜元素マッピングの測定＞
電界放射型電子顕微鏡（ＦＥ−ＳＥＭ、商品名：ＪＳＭ−７６００Ｆ、日本電子製）／エネルギー分散型スペクトロメータ（ＥＤＳ、商品名：ＮＳＳ３１２Ｅ＋ＵｌｔｒａＤｒｙ３０ｍｍ２、サーモフィッシャサイエンティフィック製）を用い、イオンミリング加工した試料断面のＣｏ元素とＭｎ元素の分布を、加速電圧１０ｋＶで測定した。
<Measurement of element mapping>
Ion milling was performed using a field emission electron microscope (FE-SEM, trade name: JSM-7600F, manufactured by JEOL) / energy dispersive spectrometer (EDS, trade name: NSS312E + UltraDry 30 mm 2 , manufactured by Thermo Fisher Scientific). The distribution of the Co element and the Mn element on the sample cross section was measured at an acceleration voltage of 10 kV.
＜電池性能評価＞
リチウム−コバルト−マンガン系複合酸化物の正極としての電池特性試験を行った。
<Battery performance evaluation>
A battery characteristic test of a lithium-cobalt-manganese composite oxide as a positive electrode was performed.
得られたリチウム−コバルト−マンガン系複合酸化物の粉末（正極活物質）と、導電助剤としてアセチレンブラック、結着剤としてＰＶＤＦを質量比で８８：６：６で混合し、ＮＭＰを加えてペースト状に調整した。このペーストを厚さ１０．７μｍのＡｌ箔集電体に塗布し、１５０℃で減圧乾燥させた。その後、φ１３ｍｍの大きさに切りだし、２ｔ／ｍ２でプレスして正極とした。得られた電池用正極と、金属リチウム箔（厚さ０ ．２ｍｍ）からなる負極、およびエチレンカーボネートとジエチルカーボネートとの混合溶媒に六フッ化リン酸リチウムを１ｍｏｌ／ｄｍ３の濃度で溶解した電解液を用いて電池を構成した。当該電池を用いて定電流で電池電圧が５．４Ｖから３．０Ｖの間、室温下で充放電させた。電流密度１０ｍＡ／ｇで充放電し、それぞれの比容量（ｍＡｈ／ｇ）を測定した。 The obtained lithium-cobalt-manganese-based composite oxide powder (positive electrode active material), acetylene black as a conductive aid, and PVDF as a binder were mixed at a mass ratio of 88: 6: 6, and NMP was added. It was adjusted to a paste. This paste was applied to a 10.7 μm-thick Al foil current collector, and dried at 150 ° C. under reduced pressure. Then, it was cut into a size of φ13 mm and pressed at 2 t / m 2 to obtain a positive electrode. Electrolysis in which lithium hexafluorophosphate is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate at a concentration of 1 mol / dm 3 in the obtained battery positive electrode, a negative electrode made of metallic lithium foil (0.2 mm in thickness), and a mixed solvent of ethylene carbonate and diethyl carbonate. A battery was constructed using the liquid. The battery was charged and discharged at room temperature at a constant current between 5.4 V and 3.0 V at a constant current. The battery was charged and discharged at a current density of 10 mA / g, and the specific capacity (mAh / g) was measured.
実施例１
硫酸コバルト及び硫酸マンガンを純水に溶解し、１．０ｍｏｌ／Ｌ（リットル）の硫酸コバルト及び１．０ｍｏｌ／Ｌの硫酸マンガンを含む水溶液（金属塩水溶液）を得た。金属塩水溶液中の全金属の合計濃度は２．０ｍｏｌ／Ｌであった。
Example 1
Cobalt sulfate and manganese sulfate were dissolved in pure water to obtain an aqueous solution (metal salt aqueous solution) containing 1.0 mol / L (liter) of cobalt sulfate and 1.0 mol / L of manganese sulfate. The total concentration of all metals in the aqueous metal salt solution was 2.0 mol / L.
また、内容積１Ｌの反応容器に純水３００ｇを入れた後、これを６０℃まで昇温し、維持した。 Further, after 300 g of pure water was charged into a reaction vessel having an internal volume of 1 L, the temperature was raised to 60 ° C. and maintained.
得られた金属塩水溶液を供給速度０．３５ｇ／ｍｉｎで反応容器に連続供給した。また、酸化剤として、空気を供給速度１Ｌ／ｍｉｎで反応容器中にバブリングした。さらに、金属塩水溶液及び空気供給の際、ｐＨが８．２５となるように、２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液（苛性ソーダ水溶液）を断続的に添加しながら連続的に反応を進行させた（反応時の酸化還元電位は０．１３Ｖであった）。前記反応により、かかる反応容器中で、コバルト−マンガン系複合化合物が析出し、スラリーが得られた。反応容器内のスラリーをろ過し、純水で洗浄することによって、ウェットケーキを得た。当該ウェットケーキを１１０℃で１５時間乾燥することで、コバルト−マンガン系複合酸化物を得た。 The obtained aqueous metal salt solution was continuously supplied to the reaction vessel at a supply rate of 0.35 g / min. In addition, air was bubbled into the reaction vessel at a supply rate of 1 L / min as an oxidizing agent. Furthermore, during the supply of the aqueous metal salt solution and the air, the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution (aqueous sodium hydroxide solution) so that the pH became 8.25. (The redox potential during the reaction was 0.13 V). By the reaction, a cobalt-manganese composite compound was precipitated in the reaction vessel, and a slurry was obtained. The slurry in the reaction vessel was filtered and washed with pure water to obtain a wet cake. By drying the wet cake at 110 ° C. for 15 hours, a cobalt-manganese composite oxide was obtained.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンを図１に示す。図１からは、２θ＝１２°付近に微弱な回折ピークがみられるものの、ほぼ立方晶スピネル型構造の単一結晶相といえた。 FIG. 1 shows an XRD pattern of the obtained cobalt-manganese composite oxide. From FIG. 1, although a weak diffraction peak is observed around 2θ = 12 °, it can be said that the single crystal phase has a substantially cubic spinel structure.
得られたコバルト−マンガン系複合酸化物の粒度分布曲線を図２に示す。図２からは、幅広い粒子径が正規分布しているといえた。 FIG. 2 shows a particle size distribution curve of the obtained cobalt-manganese composite oxide. From FIG. 2, it can be said that a wide range of particle diameters is normally distributed.
得られたコバルト−マンガン系複合酸化物の走査型電子顕微鏡写真を図３に示す。 FIG. 3 shows a scanning electron micrograph of the obtained cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．４９３Ｍｎ１．５０７Ｏ４）。 The measurement results of the obtained cobalt-manganese composite oxide are shown in Table 1 (chemical composition formula: Co 1.493 Mn 1.507 O 4 ).
実施例２
ｐＨが８．７５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．０９Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 2
A slurry was obtained in the same manner as in Example 1, except that the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 8.75 ( The oxidation-reduction potential during the reaction was 0.09 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンは図１とほぼ同じであり、２θ＝１２°付近に微弱な回折ピークがみられるものの、ほぼ立方晶スピネル型構造の単一結晶相といえた。 The XRD pattern of the obtained cobalt-manganese-based composite oxide is almost the same as FIG. 1, and although a weak diffraction peak is observed around 2θ = 12 °, it can be said that the single crystal phase has a cubic spinel structure. Was.
得られたコバルト−マンガン系複合酸化物の粒度分布曲線を図４に示す。図４からは、均一な粒子径が単分散しているといえた。 FIG. 4 shows a particle size distribution curve of the obtained cobalt-manganese composite oxide. From FIG. 4, it can be said that the uniform particle diameter is monodispersed.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．５１４Ｍｎ１．４８６Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese composite oxide (chemical composition formula: Co 1.514 Mn 1.486 O 4 ).
実施例３
ｐＨが９．００となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．１０Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 3
A slurry was obtained in the same manner as in Example 1, except that the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 9.00 ( The oxidation-reduction potential during the reaction was 0.10 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンは図１とほぼ同じであり、２θ＝１２°付近に微弱な回折ピークがみられるものの、ほぼ立方晶スピネル型構造の単一結晶相といえた。 The XRD pattern of the obtained cobalt-manganese-based composite oxide is almost the same as FIG. 1, and although a weak diffraction peak is observed around 2θ = 12 °, it can be said that the single crystal phase has a cubic spinel structure. Was.
得られたコバルト−マンガン系複合酸化物の粒度分布曲線を図５に示す。図５からは、均一な粒子径が単分散しているといえた。 FIG. 5 shows a particle size distribution curve of the obtained cobalt-manganese composite oxide. From FIG. 5, it can be said that the uniform particle diameter is monodispersed.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．５１０Ｍｎ１．４９０Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese-based composite oxide (chemical composition formula: Co 1.510 Mn 1.490 O 4 ).
実施例４
ｐＨが９．２５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．０８Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 4
A slurry was obtained in the same manner as in Example 1, except that the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 9.25 ( The oxidation-reduction potential during the reaction was 0.08 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンは図１とほぼ同じであり、立方晶スピネル型構造の単一結晶相といえた。 The XRD pattern of the obtained cobalt-manganese composite oxide was almost the same as that in FIG. 1, and it could be said that it was a single crystal phase having a cubic spinel structure.
得られたコバルト−マンガン系複合酸化物の粒度分布曲線を図６に示す。図６からは、均一な粒子径が単分散しているといえた。 FIG. 6 shows a particle size distribution curve of the obtained cobalt-manganese composite oxide. From FIG. 6, it can be said that the uniform particle size is monodispersed.
得られたコバルト−マンガン系複合酸化物の走査型電子顕微鏡写真を図７に示す。 FIG. 7 shows a scanning electron micrograph of the obtained cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．４９０Ｍｎ１．５１０Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese-based composite oxide (chemical composition formula: Co 1.490 Mn 1.510 O 4 ).
実施例５
ｐＨが８．５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させて（反応時の酸化還元電位は０．０９Ｖであった）、反応容器出口から連続的に押し出すことによってスラリーを得た以外は、実施例１と同様な方法でスラリーを得た。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 5
The reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous solution of sodium hydroxide so that the pH became 8.5 (the oxidation-reduction potential during the reaction was 0.09 V). A slurry was obtained in the same manner as in Example 1, except that the slurry was continuously extruded from the outlet of the reaction vessel. The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンを図８に示す。図８からは、立方晶スピネル型構造の単一結晶相といえた。 FIG. 8 shows an XRD pattern of the obtained cobalt-manganese composite oxide. From FIG. 8, it can be said that the single crystal phase has a cubic spinel structure.
得られたコバルト−マンガン系複合酸化物の粒度分布曲線を図９に示す。図９からは、均一な粒子径が単分散しているといえた。 FIG. 9 shows a particle size distribution curve of the obtained cobalt-manganese composite oxide. From FIG. 9, it can be said that the uniform particle diameter is monodispersed.
得られたコバルト−マンガン系複合酸化物の走査型電子顕微鏡写真を図１０に示す。 FIG. 10 shows a scanning electron micrograph of the obtained cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物の元素マッピングを図１１に示す。図１１からはＣｏ元素とＭｎ元素の偏析は認められず、高い均質性が示された。 FIG. 11 shows an element mapping of the obtained cobalt-manganese composite oxide. From FIG. 11, segregation of the Co element and the Mn element was not recognized, indicating high homogeneity.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．５１５Ｍｎ１．４８５Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese-based composite oxide (chemical composition formula: Co 1.515 Mn 1.485 O 4 ).
実施例６
ｐＨが９．５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．０８Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 6
A slurry was obtained in the same manner as in Example 1 except that the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 9.5 ( The oxidation-reduction potential during the reaction was 0.08 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンを図１２に示す。図１２からは、２θ＝３４°付近および２θ＝６６°付近にオキシ水酸化物に対応する弱い回折ピークがみられたため、立方晶スピネル型構造が主相で、オキシ水酸化物型構造が副相であるといえた。また、２θ＝１８．５°±１．０°の回折ピークの強度が実施例１〜５に比べて明らかに強いことからも、オキシ水酸化物相の存在が確認できた。 FIG. 12 shows an XRD pattern of the obtained cobalt-manganese composite oxide. From FIG. 12, weak diffraction peaks corresponding to the oxyhydroxide were observed at around 2θ = 34 ° and around 2θ = 66 °, so that the cubic spinel structure was the main phase and the oxyhydroxide structure was the subphase. It was a phase. The presence of the oxyhydroxide phase was also confirmed from the fact that the intensity of the diffraction peak at 2θ = 18.5 ° ± 1.0 ° was clearly higher than in Examples 1 to 5.
立方晶スピネル型構造の結晶相比率は他の副相に比べ高いことは明らかであった。 It was clear that the crystal phase ratio of the cubic spinel structure was higher than the other subphases.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．５０８Ｍｎ１．４９２Ｏ４）。 The measurement results of the obtained cobalt-manganese composite oxide are shown in Table 1 (chemical composition formula: Co 1.508 Mn 1.492 O 4 ).
実施例７
ｐＨが９．７５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．０９Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 7
A slurry was obtained in the same manner as in Example 1, except that the reaction was allowed to proceed continuously while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 9.75 ( The oxidation-reduction potential during the reaction was 0.09 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンは図１２とほぼ同じであり、２θ＝３４°付近および２θ＝６６°付近にオキシ水酸化物に対応する弱い回折ピークがみられたため、立方晶スピネル型構造が主相で、オキシ水酸化物型構造が副相であるといえた。立方晶スピネル型構造の結晶相比率は他の副相に比べ高いことは明らかであった。 The XRD pattern of the obtained cobalt-manganese-based composite oxide is almost the same as FIG. 12, and weak diffraction peaks corresponding to oxyhydroxide were observed at around 2θ = 34 ° and around 2θ = 66 °. The crystal spinel structure was the main phase, and the oxyhydroxide structure was the sub phase. It was clear that the crystal phase ratio of the cubic spinel structure was higher than the other subphases.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．５１８Ｍｎ１．４８２Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese composite oxide (chemical composition formula: Co 1.518 Mn 1.482 O 4 ).
実施例８
ｐＨが１０．２５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は０．０５Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 8
A slurry was obtained in the same manner as in Example 1, except that the reaction was continuously performed while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 10.25 ( The oxidation-reduction potential during the reaction was 0.05 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンは図１２とほぼ同じであり、２θ＝３４°付近および２θ＝６６°付近にオキシ水酸化物に対応する弱い回折ピークがみられたため、立方晶スピネル型構造が主相で、オキシ水酸化物型構造が副相であるといえた。立方晶スピネル型構造の結晶相比率は他の副相に比べ高いことは明らかであった。 The XRD pattern of the obtained cobalt-manganese-based composite oxide is almost the same as FIG. 12, and weak diffraction peaks corresponding to oxyhydroxide were observed at around 2θ = 34 ° and around 2θ = 66 °. The crystal spinel structure was the main phase, and the oxyhydroxide structure was the sub phase. It was clear that the crystal phase ratio of the cubic spinel structure was higher than the other subphases.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．４９６Ｍｎ１．５０４Ｏ４）。 Table 1 shows the measurement results of the obtained cobalt-manganese-based composite oxide (chemical composition formula: Co 1.496 Mn 1.504 O 4 ).
実施例９
ｐＨが１１．２５となるように２．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を断続的に添加しながら連続的に反応を進行させた以外は、実施例１と同様な方法でスラリーを得た（反応時の酸化還元電位は−０．０１Ｖであった）。得られたスラリーを、実施例１と同様にして、ろ過し、洗浄した後、乾燥することで、コバルト−マンガン系複合酸化物を得た。
Example 9
A slurry was obtained in the same manner as in Example 1 except that the reaction was continuously progressed while intermittently adding a 2.5 mol / L aqueous sodium hydroxide solution so that the pH became 11.25 ( The oxidation-reduction potential during the reaction was -0.01 V). The obtained slurry was filtered, washed and dried in the same manner as in Example 1 to obtain a cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物のＸＲＤパターンを図１３に示す。図１３からは、立方晶スピネル型構造が主相で、オキシ水酸化物型構造およびハイドロタルサイト型酸化物構造が副相であるといえた。 FIG. 13 shows an XRD pattern of the obtained cobalt-manganese composite oxide. From FIG. 13, it can be said that the cubic spinel type structure is the main phase, and the oxyhydroxide type structure and the hydrotalcite type oxide structure are the sub phases.
得られたコバルト−マンガン系複合酸化物の走査型電子顕微鏡写真を図１４に示す。 FIG. 14 shows a scanning electron micrograph of the obtained cobalt-manganese composite oxide.
得られたコバルト−マンガン系複合酸化物の測定結果を表１に示す（化学組成式：Ｃｏ１．４７９Ｍｎ１．５２１Ｏ４）。 The measurement results of the obtained cobalt-manganese-based composite oxide are shown in Table 1 (chemical composition formula: Co 1.479 Mn 1.521 O 4 ).
実施例１０
実施例５で得られたコバルト−マンガン系複合酸化物と炭酸リチウムを混合し、空気流中、９００℃で１２時間焼成した後、７００℃で２４時間、６５０℃で２４時間、６００℃で２４時間アニールすることにより、リチウム−コバルト−マンガン系複合酸化物を得た。化学組成分析の結果から、組成式：ＬｉＣｏＭｎＯ４と表すことができた。
Example 10
The cobalt-manganese-based composite oxide obtained in Example 5 and lithium carbonate were mixed, and calcined in an air stream at 900 ° C for 12 hours, and then at 700 ° C for 24 hours, 650 ° C for 24 hours, and 600 ° C for 24 hours. By annealing for a time, a lithium-cobalt-manganese composite oxide was obtained. From the result of the chemical composition analysis, it could be expressed as a composition formula: LiCoMnO 4 .
得られたリチウム−コバルト−マンガン系複合酸化物のＸＲＤパターンを図１５に示す。図１５からは、空間群Ｆｄ−３ｍに帰属される立方晶スピネル型構造であるといえた。 FIG. 15 shows an XRD pattern of the obtained lithium-cobalt-manganese composite oxide. From FIG. 15, it can be said that the structure is a cubic spinel structure belonging to the space group Fd-3m.
得られたリチウム−コバルト−マンガン系複合酸化物の電池性能評価の結果を表２に示す。表２から、４．７Ｖ以上の放電容量が大きく、高エネルギー密度を有していることが示された。 Table 2 shows the results of the battery performance evaluation of the obtained lithium-cobalt-manganese composite oxide. Table 2 shows that the discharge capacity of 4.7 V or more is large and has a high energy density.
本発明のコバルト−マンガン系複合酸化物は、リチウム二次電池の正極活物質などに用いられるリチウム−コバルト−マンガン系複合酸化物の前駆体として使用することができ、そのリチウム−コバルト−マンガン系複合酸化物を電池用正極として使用した高性能なリチウム二次電池を構成することが可能となる。 The cobalt-manganese composite oxide of the present invention can be used as a precursor of a lithium-cobalt-manganese composite oxide used for a positive electrode active material of a lithium secondary battery, and the lithium-cobalt-manganese composite oxide A high-performance lithium secondary battery using the composite oxide as a battery positive electrode can be configured.
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