JP2008013419A - Method for producing lithium composite metal oxide - Google Patents
Method for producing lithium composite metal oxide Download PDFInfo
- Publication number
- JP2008013419A JP2008013419A JP2006189004A JP2006189004A JP2008013419A JP 2008013419 A JP2008013419 A JP 2008013419A JP 2006189004 A JP2006189004 A JP 2006189004A JP 2006189004 A JP2006189004 A JP 2006189004A JP 2008013419 A JP2008013419 A JP 2008013419A
- Authority
- JP
- Japan
- Prior art keywords
- composite metal
- metal oxide
- lithium composite
- producing
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 56
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 47
- 239000003513 alkali Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 31
- -1 LiOH anhydride Chemical class 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 5
- 150000004687 hexahydrates Chemical class 0.000 description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 5
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 150000004677 hydrates Chemical class 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
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001786 chalcogen compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- ZYAMKYAPIQPWQR-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-3-methoxypropane Chemical compound COCC(F)(F)C(F)(F)F ZYAMKYAPIQPWQR-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- PCTQNZRJAGLDPD-UHFFFAOYSA-N 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane Chemical compound FC(F)OCC(F)(F)C(F)F PCTQNZRJAGLDPD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
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- 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
- 239000011565 manganese chloride Substances 0.000 description 2
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- 229940099607 manganese chloride Drugs 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 235000002639 sodium chloride Nutrition 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 235000012501 ammonium carbonate Nutrition 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム複合金属酸化物の製造方法に関する。 The present invention relates to a method for producing a lithium composite metal oxide.
リチウム複合金属酸化物は、リチウム二次電池などの非水電解質二次電池の正極に用いられている。リチウム二次電池は、既に携帯電話やノートパソコン等の電源として実用化されており、更に自動車用途や電力貯蔵用途などの中・大型用途においても、適用が試みられている。 Lithium composite metal oxides are used for positive electrodes of nonaqueous electrolyte secondary batteries such as lithium secondary batteries. Lithium secondary batteries have already been put into practical use as power sources for mobile phones, notebook computers, etc., and are also being applied to medium and large applications such as automobile applications and power storage applications.
従来のリチウム二次電池に用いられているリチウム複合金属酸化物として、特許文献１には、リチウム−ニッケル−マンガン−Ｍ複合酸化物（ＭはＦｅ、Ｃｏ、Ｃｒ、Ａｌ）が開示され、ニッケルとマンガンを含有する混合水溶液にアルカリを加えて得られるニッケル−マンガン共沈水酸化物を用いて合成したリチウム複合金属酸化物（ＬｉＮｉ0.5Ｍｎ0.5Ｏ2）を用いたリチウム二次電池は、その充放電サイクル試験時の容量維持率が９２％であったことが具体的に記載されている。 As a lithium composite metal oxide used in a conventional lithium secondary battery, Patent Document 1 discloses a lithium-nickel-manganese-M composite oxide (M is Fe, Co, Cr, Al). A lithium secondary battery using a lithium composite metal oxide (LiNi 0.5 Mn 0.5 O 2 ) synthesized using nickel-manganese coprecipitated hydroxide obtained by adding an alkali to a mixed aqueous solution containing manganese and manganese is It is specifically described that the capacity retention rate during the discharge cycle test was 92%.
しかしながら、従来のリチウム二次電池の容量維持率は十分なものではない。本発明の目的は、従来より高い容量維持率を示すことが可能な非水電解質二次電池に有用なリチウム複合金属酸化物の製造方法を提供することにある。 However, the capacity maintenance rate of the conventional lithium secondary battery is not sufficient. An object of the present invention is to provide a method for producing a lithium composite metal oxide useful for a non-aqueous electrolyte secondary battery capable of exhibiting a higher capacity retention rate than before.
本発明者らは、種々検討した結果、上記目的に合致する製造方法を見出し、本発明に至った。 As a result of various studies, the present inventors have found a production method that meets the above-mentioned purpose, and have reached the present invention.
すなわち本発明は、下記の発明から構成される。
＜１＞Ｌｉ、ＮｉおよびＭ（ここで、ＭはＭｎおよび／またはＣｏを表わす。）を含有するリチウム複合金属酸化物の製造方法であって、以下の（１）、（２）、（３）および（４）の工程をこの順で含むリチウム複合金属酸化物の製造方法。
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤と、ＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（４）該洗浄品を乾燥し、乾燥品を得る工程。
＜２＞さらに、以下の（５）の工程を含む前記＜１＞記載のリチウム複合金属酸化物の製造方法。
（５）上記乾燥品を焼成し、焼成品を得る工程。
＜３＞さらに、以下の（６）の工程を含む前記＜１＞記載のリチウム複合金属酸化物の製造方法。
（６）上記乾燥品とリチウム塩とを混合して得られる混合物を焼成し、焼成品を得る工程。
＜４＞Ｌｉ、ＮｉおよびＭ（ここで、ＭはＭｎおよび／またはＣｏを表わす。）を含有するリチウム複合金属酸化物の製造方法であって、以下の（１）、（２）、（３）および（７）の工程を含むリチウム複合金属酸化物の製造方法。
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤とＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（７）該洗浄品とリチウム塩とを混合して得られる混合物を焼成し、焼成品を得る工程。
＜５＞焼成が、３００℃以上１０００℃以下の温度範囲でなされる前記＜２＞〜＜４＞のいずれかに記載のリチウム複合金属酸化物の製造方法。
＜６＞ＭがＭｎである前記＜１＞〜＜５＞のいずれかに記載のリチウム複合金属酸化物の製造方法。
＜７＞アルカリ（Ａ）がＬｉＯＨの無水物および／または水和物である前記＜１＞〜＜６＞のいずれかに記載のリチウム複合金属酸化物の製造方法。
＜８＞酸化剤がＫＣｌＯ3である前記＜１＞〜＜７＞のいずれかに記載のリチウム複合金属酸化物の製造方法。
＜９＞アルカリ（Ｂ）がさらにＫＯＨを含む前記＜１＞〜＜８＞のいずれかに記載のリチウム複合金属酸化物の製造方法。
That is, this invention is comprised from the following invention.
<1> A method for producing a lithium composite metal oxide containing Li, Ni and M (wherein M represents Mn and / or Co), comprising the following (1), (2), (3 ) And (4) in this order, a method for producing a lithium composite metal oxide.
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent, and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(4) A step of drying the washed product to obtain a dried product.
<2> The method for producing a lithium composite metal oxide according to <1>, further including the following step (5).
(5) A step of firing the dried product to obtain a fired product.
<3> The method for producing a lithium composite metal oxide according to <1>, further including the following step (6).
(6) The process of baking the mixture obtained by mixing the said dried product and lithium salt, and obtaining a baked product.
<4> A method for producing a lithium composite metal oxide containing Li, Ni, and M (wherein M represents Mn and / or Co), comprising the following (1), (2), (3 ) And (7), a method for producing a lithium composite metal oxide.
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(7) A step of firing the mixture obtained by mixing the washed product and the lithium salt to obtain a fired product.
<5> The method for producing a lithium composite metal oxide according to any one of <2> to <4>, wherein the firing is performed in a temperature range of 300 ° C. or higher and 1000 ° C. or lower.
<6> The method for producing a lithium composite metal oxide according to any one of <1> to <5>, wherein M is Mn.
<7> The method for producing a lithium composite metal oxide according to any one of <1> to <6>, wherein the alkali (A) is an anhydride and / or hydrate of LiOH.
<8> The method for producing a lithium composite metal oxide according to any one of <1> to <7>, wherein the oxidizing agent is KClO 3 .
<9> The method for producing a lithium composite metal oxide according to any one of <1> to <8>, wherein the alkali (B) further contains KOH.
本発明の製造方法によれば、従来のリチウム二次電池に比し、容量維持率が向上した非水電解質二次電池に有用なリチウム複合金属酸化物を得ることができることから、殊に、高い電流レートにおける高出力を要求される非水電解質二次電池、すなわち自動車用や電動工具等のパワーツール用の非水電解質二次電池の製造に極めて有用となる。 According to the production method of the present invention, it is possible to obtain a lithium composite metal oxide useful for a nonaqueous electrolyte secondary battery having an improved capacity retention rate as compared with a conventional lithium secondary battery. This is extremely useful for the production of nonaqueous electrolyte secondary batteries that require high output at a current rate, that is, nonaqueous electrolyte secondary batteries for power tools such as automobiles and electric tools.
本発明のリチウム複合金属酸化物の製造方法は、Ｌｉ、ＮｉおよびＭ（ここで、ＭはＭｎおよび／またはＣｏを表わす。）を含有するリチウム複合金属酸化物の製造方法であって、以下の（１）、（２）、（３）および（４）の工程をこの順で含むことを特徴とする。
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤と、ＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（４）該洗浄品を乾燥し、乾燥品を得る工程。
The method for producing a lithium composite metal oxide according to the present invention is a method for producing a lithium composite metal oxide containing Li, Ni and M (where M represents Mn and / or Co), (1), (2), (3) and (4) are included in this order.
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent, and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(4) A step of drying the washed product to obtain a dried product.
工程（１）におけるＮｉおよびＭ（ただし、ＭはＭｎおよび／またはＣｏである。）を含有する水溶液は、水溶液中に、ＮｉおよびＭを含有していればよく、原料として、Ｎｉ、Ｍを含有する化合物で、塩化物、硝酸塩、硫酸塩、シュウ酸塩、酢酸塩などの水溶性化合物を用いる場合には、該化合物を水に溶解させて製造すればよい。これらの水溶性化合物は、無水物および水和物のいずれであってもよい。また、原料として、Ｍｉ、Ｍの金属材料や、Ｎｉ、Ｍを含有する化合物で、水酸化物、酸水酸化物、酸化物などの水への溶解が困難な化合物を用いる場合には、これらを塩酸などの酸に溶解させて製造すればよい。また、Ｎｉ、Ｍそれぞれについて、上述の水溶性化合物、水への溶解が困難な化合物、金属材料のうち２種以上を併用してもよい。 The aqueous solution containing Ni and M (wherein M is Mn and / or Co) in the step (1) only needs to contain Ni and M in the aqueous solution. In the case of using a water-soluble compound such as chloride, nitrate, sulfate, oxalate, and acetate as the compound to be contained, the compound may be prepared by dissolving it in water. These water-soluble compounds may be either anhydrides or hydrates. In addition, when using a compound containing Mi, M, or Ni, M as a raw material and difficult to dissolve in water, such as a hydroxide, an acid hydroxide, or an oxide, these are used. May be dissolved in an acid such as hydrochloric acid. Further, for each of Ni and M, two or more of the aforementioned water-soluble compounds, compounds difficult to dissolve in water, and metal materials may be used in combination.
工程（１）におけるアルカリ（Ａ）としては、ＬｉＯＨ（水酸化リチウム）、ＮａＯＨ（水酸化ナトリウム）、ＫＯＨ（水酸化カリウム）、ＮＨ3（アンモニア）、Ｎａ2ＣＯ3（炭酸ナトリウム）、Ｋ2ＣＯ3（炭酸カリウム）および（ＮＨ4）2ＣＯ3（炭酸アンモニウム）からなる群より選ばれる１種以上の無水物および／または該１種以上の水和物を用いることができ、通常、これらを水に溶解させて、水溶液として用いる。該水溶液におけるアルカリ（Ａ）の濃度は、通常０．１〜２０Ｍ程度、好ましくは０．５〜１０Ｍ程度である。また、リチウム複合金属酸化物における不純物を減らす観点から、アルカリ（Ａ）として、ＬｉＯＨの無水物および／または水和物を用いることが好ましい。また、製造コストの面からは、アルカリ（Ａ）としてＫＯＨの無水物および／または水和物を用いることが好ましい。また、これらのアルカリ（Ａ）を２つ以上併用してもよい。 As the alkali (A) in the step (1), LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), NH 3 (ammonia), Na 2 CO 3 (sodium carbonate), K 2 One or more anhydrides and / or one or more hydrates selected from the group consisting of CO 3 (potassium carbonate) and (NH 4 ) 2 CO 3 (ammonium carbonate) can be used. Is dissolved in water and used as an aqueous solution. The concentration of alkali (A) in the aqueous solution is usually about 0.1 to 20M, preferably about 0.5 to 10M. Further, from the viewpoint of reducing impurities in the lithium composite metal oxide, it is preferable to use LiOH anhydride and / or hydrate as the alkali (A). Further, from the viewpoint of production cost, it is preferable to use an anhydride and / or hydrate of KOH as the alkali (A). Two or more of these alkalis (A) may be used in combination.
工程（１）において、上記のＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させるときには、例えば、ＮｉおよびＭを含有する水溶液にアルカリ（Ａ）を添加する。このとき、ＮｉおよびＭを含有する水溶液を攪拌しておくことが好ましい。粒径が均一な沈殿を得るために、ＮｉおよびＭを含有する水溶液を攪拌しながら、アルカリ（Ａ）の水溶液を滴下することがより好ましい。この場合、ＮｉおよびＭを含有する水溶液を攪拌しながら、該水溶液のｐＨの計測を開始し、アルカリ（Ａ）の水溶液を滴下するに従い、計測ｐＨが上昇していく傾向にあるが、計測ｐＨが１１以上となるまで、アルカリ（Ａ）の水溶液を滴下するのがよい。また添加するアルカリ（Ａ）の量を把握しているときには、アルカリ（Ａ）の水溶液に、ＮｉおよびＭを含有する水溶液を添加することにより、沈殿を生成させてもよい。 In the step (1), when the precipitate is formed by mixing the aqueous solution containing Ni and M and the alkali (A), for example, the alkali (A) is added to the aqueous solution containing Ni and M. . At this time, it is preferable to stir the aqueous solution containing Ni and M. In order to obtain a precipitate having a uniform particle size, it is more preferable to add an alkaline (A) aqueous solution dropwise while stirring the aqueous solution containing Ni and M. In this case, while stirring the aqueous solution containing Ni and M, the measurement of the pH of the aqueous solution is started, and the measured pH tends to increase as the alkali (A) aqueous solution is dropped. It is preferable to drop an aqueous solution of alkali (A) until 11 becomes 11 or more. Further, when the amount of alkali (A) to be added is known, precipitation may be generated by adding an aqueous solution containing Ni and M to the aqueous solution of alkali (A).
また、沈殿生成を均一に行う意味で、ＮｉおよびＭを含有する水溶液および／またはアルカリ（Ａ）の水溶液を冷却して用いてもよい。この冷却のときの温度としては、１０℃以下が好ましく、より好ましくは−１５℃以上５℃以下程度である。冷却の温度を０℃以下とする場合には、不凍液としてメタノール、エタノール、エチレングリコールなど、水１００重量部に対し、不凍液１〜５０重量部の割合でＮｉおよびＭを含有する水溶液および／またはアルカリ（Ａ）の水溶液に添加してもよい。 In addition, an aqueous solution containing Ni and M and / or an aqueous solution of alkali (A) may be used after cooling in order to uniformly precipitate. The temperature at the time of cooling is preferably 10 ° C. or lower, more preferably about −15 ° C. or higher and 5 ° C. or lower. When the cooling temperature is 0 ° C. or less, an aqueous solution and / or an alkali containing Ni and M in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of water such as methanol, ethanol or ethylene glycol as an antifreeze. You may add to the aqueous solution of (A).
本発明の効果をより上げる意味で、上記のＮｉおよびＭを含有する水溶液中に、空気等の酸素含有ガスを導入する操作をしながら、アルカリ（Ａ）を添加してもよい。アルカリ（Ａ）の水溶液中に、ＮｉおよびＭを含有する水溶液を添加する場合には、アルカリ（Ａ）の水溶液中に、ガスを導入する操作を行うのがよい。また、混合後に、該操作を行ってもよい。該操作の時間としては、１時間〜５日程度、温度としては、０〜１００℃程度である。 In order to further improve the effect of the present invention, alkali (A) may be added to the above aqueous solution containing Ni and M while introducing an oxygen-containing gas such as air. When an aqueous solution containing Ni and M is added to an aqueous solution of alkali (A), an operation of introducing a gas into the aqueous solution of alkali (A) is preferably performed. Moreover, you may perform this operation after mixing. The operation time is about 1 hour to 5 days, and the temperature is about 0 to 100 ° C.
工程（１）における混合により、生成された沈殿を有する混合液について、ろ過等の固液分離を行う場合には、混合液を固液分離し得られる沈殿を再度水に分散させて得られる分散液を、工程（２）で用いる。固液分離し得られる沈殿について、洗浄を行ってもよい。また、生成された沈殿を有する混合液を、固液分離を行うことなしに、そのまま工程（２）で用いてもよい。 In the case of performing solid-liquid separation such as filtration on the mixed liquid having the precipitate produced by the mixing in the step (1), the dispersion obtained by dispersing the precipitate obtained by solid-liquid separation of the mixed liquid in water again. The liquid is used in step (2). You may wash about the precipitate obtained by solid-liquid separation. Moreover, you may use the liquid mixture which has the produced | generated precipitation in process (2) as it is, without performing solid-liquid separation.
工程（２）において、液状混合物は、工程（１）で得られた沈殿と酸化剤とＬｉＯＨを含むアルカリ（Ｂ）とを含有するものである。酸化剤は、液状混合物中の金属元素を酸化するのに用いる。酸化剤としては、ＮａＣｌＯ（次亜塩素酸ナトリウム）、ＨＮＯ3（硝酸）、ＫＣｌＯ3（塩素酸カリウム）およびＨ2Ｏ2（過酸化水素）からなる群より選ばれる１種以上を挙げることができ、製造コスト、酸化反応性の面では、Ｈ2Ｏ2および／またはＫＣｌＯ3が好ましく、酸化反応制御をし易くする意味でより好ましいのはＫＣｌＯ3である。また、ＬｉＯＨを含むアルカリ（Ｂ）としては、ＬｉＯＨの無水物および／または水和物のみか、さらにＮａＯＨの無水物および／または水和物、ＫＯＨの無水物および／または水和物、好ましくはＫＯＨの無水物および／または水和物を含有してもよい。これらの酸化剤およびアルカリ（Ｂ）を、上記の混合液または分散液に添加して、液状混合物を製造することができる。液状混合物中の酸化剤の濃度は、通常０．１〜１０Ｍ程度、好ましくは０．３〜５Ｍ程度であり、液状混合物中のアルカリ（Ｂ）は、通常０．１〜３０Ｍ程度、好ましくは、１〜２０Ｍ程度であり、液状混合物中の沈殿の含有量は通常１〜２００ｇ／（液体混合物１Ｌ）程度である。また、液状混合物におけるＬｉの濃度は、０．１〜１０Ｍとしておくことが好ましく、０．５〜５Ｍとしておくことがより好ましい。液状混合物は、必要に応じて、塩化リチウム、硝酸リチウム、炭酸リチウムを含有してもよい。また、液状混合物のｐＨは、水熱処理における反応を促進させる意味で、１１以上であることが好ましく、１３以上であることがより好ましい。 In the step (2), the liquid mixture contains the precipitate obtained in the step (1), an oxidizing agent, and an alkali (B) containing LiOH. The oxidizing agent is used to oxidize metal elements in the liquid mixture. Examples of the oxidizing agent include one or more selected from the group consisting of NaClO (sodium hypochlorite), HNO 3 (nitric acid), KClO 3 (potassium chlorate), and H 2 O 2 (hydrogen peroxide). can, manufacturing cost, in terms of oxidation resistance, preferably H 2 O 2 and / or KClO 3, and more preferably in the sense that to facilitate the oxidation reaction control is KClO 3. In addition, as the alkali (B) containing LiOH, only LiOH anhydride and / or hydrate, NaOH anhydride and / or hydrate, KOH anhydride and / or hydrate, preferably KOH anhydrides and / or hydrates may be included. A liquid mixture can be produced by adding these oxidizing agent and alkali (B) to the above mixture or dispersion. The concentration of the oxidizing agent in the liquid mixture is usually about 0.1 to 10M, preferably about 0.3 to 5M, and the alkali (B) in the liquid mixture is usually about 0.1 to 30M, preferably The content of the precipitate in the liquid mixture is usually about 1 to 200 g / (liquid mixture 1 L). The concentration of Li in the liquid mixture is preferably 0.1 to 10M, and more preferably 0.5 to 5M. The liquid mixture may contain lithium chloride, lithium nitrate, or lithium carbonate as necessary. The pH of the liquid mixture is preferably 11 or more, more preferably 13 or more, in order to promote the reaction in the hydrothermal treatment.
工程（２）において上記の液状混合物を用いて、１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る。この温度範囲における圧力は、通常、０．４ＭＰａ〜１７ＭＰａ程度である。水熱処理装置としては、オートクレーブを用いればよい。水熱処理の好ましい温度範囲としては、１８０℃〜２５０℃である。水熱処理の時間としては、通常０．１〜１５０時間程度であり、好ましくは０．５〜５０時間である。 In the step (2), the liquid mixture is hydrothermally treated in the temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product. The pressure in this temperature range is usually about 0.4 MPa to 17 MPa. An autoclave may be used as the hydrothermal treatment apparatus. A preferable temperature range for the hydrothermal treatment is 180 ° C to 250 ° C. The hydrothermal treatment time is usually about 0.1 to 150 hours, preferably 0.5 to 50 hours.
工程（３）において、水熱処理品を洗浄する。この洗浄により、水熱処理品中の例えば水酸化リチウム、塩化リチウム、硝酸リチウム、炭酸リチウム、酸化剤等の不純物を除去することができる。洗浄は、通常、水熱処理品をろ過等により固液分離後に得られる固形分を、水、水−アルコール、アセトンなどにより洗浄し、再度、固液分離する。固液分離後の固形分が、洗浄品である。 In step (3), the hydrothermally treated product is washed. By this washing, impurities such as lithium hydroxide, lithium chloride, lithium nitrate, lithium carbonate, and oxidizing agent in the hydrothermally treated product can be removed. In washing, the solid content obtained after the solid-liquid separation of the hydrothermally treated product by filtration or the like is usually washed with water, water-alcohol, acetone or the like, and solid-liquid separated again. The solid content after the solid-liquid separation is a washed product.
工程（４）において、洗浄品を乾燥し、乾燥品を得る。この乾燥は、通常、熱処理によって行うが、送風乾燥、真空乾燥等によってもよい。熱処理によって行う場合には、通常５０〜３００℃で行い、好ましくは１００℃〜２００℃程度である。工程（４）において得られる乾燥品は、本発明におけるリチウム複合金属化合物である。 In step (4), the washed product is dried to obtain a dried product. This drying is usually performed by heat treatment, but may be performed by air drying, vacuum drying, or the like. When performing by heat processing, it is normally performed at 50-300 degreeC, Preferably it is about 100 degreeC-200 degreeC. The dried product obtained in the step (4) is the lithium composite metal compound in the present invention.
また、本発明の製造方法においては、さらに、以下の（５）または（６）の工程を付加することが好ましい。
（５）上記の乾燥品を焼成し、焼成品を得る工程。
（６）上記の乾燥品とリチウム化合物とを混合して得られる混合物を焼成し、焼成品を得る工程。
In the production method of the present invention, it is preferable to further add the following step (5) or (6).
(5) A step of firing the dried product to obtain a fired product.
(6) A step of firing a mixture obtained by mixing the dried product and the lithium compound to obtain a fired product.
また、以下の（１）、（２）、（３）および（７）の工程を含む製法によって、リチウム複合金属酸化物を製造してもよい。ここで、以下の（１）、（２）および（３）の工程は、上記と同じ意味を有する。
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤とＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（７）該洗浄品とリチウム塩とを混合して得られる混合物を焼成し、焼成品を得る工程。
Moreover, you may manufacture a lithium composite metal oxide with the manufacturing method including the process of the following (1), (2), (3) and (7). Here, the following steps (1), (2) and (3) have the same meaning as described above.
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(7) A step of firing the mixture obtained by mixing the washed product and the lithium salt to obtain a fired product.
焼成品を得る工程がある場合には、焼成品は、本発明におけるリチウム複合金属化合物である。焼成を行うことにより、リチウム複合金属化合物の結晶性が向上し、初期放電容量が大きくなる場合がある。 When there is a step of obtaining a fired product, the fired product is the lithium composite metal compound in the present invention. By performing the firing, the crystallinity of the lithium composite metal compound may be improved and the initial discharge capacity may be increased.
工程（５）、（６）または（７）において、焼成の温度は、３００℃以上１０００℃以下であることが好ましく、より好ましくは５００℃以上９００℃以下である。前記焼成温度で保持する時間は、通常０．１〜２０時間であり、好ましくは０．５〜８時間である。前記焼成温度までの昇温速度は、通常５０℃〜４００℃／時間であり、前記焼成温度から室温までの降温速度は、通常１０℃〜４００℃／時間である。また、焼成の雰囲気としては、空気、酸素、窒素、アルゴンまたはそれらの混合ガスを用いることができるが、酸素が含まれている雰囲気が好ましい。 In the step (5), (6) or (7), the firing temperature is preferably 300 ° C. or higher and 1000 ° C. or lower, more preferably 500 ° C. or higher and 900 ° C. or lower. The time for holding at the firing temperature is usually 0.1 to 20 hours, preferably 0.5 to 8 hours. The rate of temperature rise to the firing temperature is usually 50 ° C. to 400 ° C./hour, and the rate of temperature fall from the firing temperature to room temperature is usually 10 ° C. to 400 ° C./hour. As the firing atmosphere, air, oxygen, nitrogen, argon, or a mixed gas thereof can be used, but an atmosphere containing oxygen is preferable.
工程（６）または（７）におけるリチウム塩としては、水酸化リチウム、塩化リチウム、硝酸リチウムおよび炭酸リチウムからなる群より選ばれる１種以上の無水物および／または該１種以上の水和物を挙げることができる。乾燥品または洗浄品とリチウム塩との混合方法には、乾式混合法、湿式混合法のいずれを用いることができるが、混合をより均一にする意味では、湿式混合法であることが好ましい。この場合、湿式混合法は、乾燥品または洗浄品とリチウム塩を含有する水溶液とを混合する場合も含む。混合装置としては、攪拌混合、Ｖ型混合機、Ｗ型混合機、リボン混合機、ドラムミキサー、ボールミル等を挙げることができる。また、工程（６）または（７）における混合物を焼成前に乾燥してもよい。 The lithium salt in step (6) or (7) includes one or more anhydrides selected from the group consisting of lithium hydroxide, lithium chloride, lithium nitrate and lithium carbonate and / or the one or more hydrates. Can be mentioned. Either a dry mixing method or a wet mixing method can be used as a method for mixing the dried product or the washed product with the lithium salt, but the wet mixing method is preferable in terms of making the mixing more uniform. In this case, the wet mixing method includes a case where a dry product or a cleaned product is mixed with an aqueous solution containing a lithium salt. Examples of the mixing device include stirring and mixing, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, a ball mill, and the like. Moreover, you may dry the mixture in process (6) or (7) before baking.
以上の方法により得られたリチウム複合金属化合物を、ボールミルやジェットミルなどを用いて粉砕してもよいし、粉砕と焼成を２回以上繰り返してもよい。得られたリチウム複合金属化合物は必要に応じて洗浄あるいは分級することもできる。 The lithium composite metal compound obtained by the above method may be pulverized using a ball mill or a jet mill, or pulverization and firing may be repeated twice or more. The obtained lithium composite metal compound can be washed or classified as required.
本発明の製造方法により得られるリチウム複合金属酸化物の組成において、ＮｉとＭとの組成としては、ＮｉおよびＭの合計量（モル）に対し、Ｍの量（モル）が０を超え０．９以下である場合が、容量維持率をより大きくすることができる意味で好ましい。 In the composition of the lithium composite metal oxide obtained by the production method of the present invention, the composition of Ni and M is such that the amount (mole) of M exceeds 0 and is 0. 9 or less is preferable in the sense that the capacity retention ratio can be further increased.
また、Ｍ、すなわちＭｎおよびＣｏの組成としては、ＭｎおよびＣｏの合計量（モル）に対し、Ｃｏの量（モル）が０以上０．４以下である場合が、容量維持率をより大きくすることができる意味で好ましい。 Further, as the composition of M, that is, Mn and Co, when the amount (mole) of Co is 0 or more and 0.4 or less with respect to the total amount (mole) of Mn and Co, the capacity retention ratio is further increased It is preferable in the sense that it can be.
また、Ｌｉ、ＮｉおよびＭの組成としては、（Ｎｉ＋Ｍ）との合計量（モル）に対し、Ｌｉの量（モル）が０．６以上１．５以下である場合が、容量維持率をより大きくすることができる意味で好ましく、より好ましくは１．０以上１．４以下である。 Moreover, as a composition of Li, Ni and M, when the amount (mol) of Li is 0.6 or more and 1.5 or less with respect to the total amount (mol) with (Ni + M), the capacity retention rate is more It is preferable in the meaning which can be enlarged, More preferably, it is 1.0 or more and 1.4 or less.
また、本発明の効果を損なわない範囲で、リチウム複合金属酸化物のＬｉ、Ｎｉ、Ｃｏ、Ｍｎの一部をＢ、Ａｌ、Ｇａ、Ｉｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｍｇ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｔｃ、Ｒｕ、Ｒｈ、Ｉｒ、Ｐｄ、Ｃｕ、Ａｇ、Ｚｎ等の元素で置換してもよい。 In addition, a part of Li, Ni, Co, and Mn of the lithium composite metal oxide may be replaced with B, Al, Ga, In, Si, Ge, Sn, Mg, Sc, Y, and Ti within a range not impairing the effects of the present invention. , Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Ru, Rh, Ir, Pd, Cu, Ag, Zn and the like may be substituted.
本発明の製造方法により得られるリチウム複合金属酸化物の結晶構造は、通常、層状岩塩型結晶構造、すなわち、ＮａＦｅＯ2型結晶構造であり、該結晶構造は、粉末Ｘ線回折測定により、測定することができる。 The crystal structure of the lithium composite metal oxide obtained by the production method of the present invention is usually a layered rock salt crystal structure, that is, a NaFeO 2 crystal structure, and the crystal structure is measured by powder X-ray diffraction measurement. be able to.
なお、本発明により得られるリチウム複合金属酸化物のＢＥＴ比表面積は、通常３ｍ2／ｇ以上３０ｍ2／ｇ以下程度である。 In addition, the BET specific surface area of the lithium composite metal oxide obtained by the present invention is usually about 3 m 2 / g or more and 30 m 2 / g or less.
本発明の製造方法により得られるリチウム複合金属酸化物を、リチウム二次電池の正極活物質として用いて、例えば、次のようにして、リチウム二次電池を製造することができる。 Using the lithium composite metal oxide obtained by the production method of the present invention as a positive electrode active material of a lithium secondary battery, for example, a lithium secondary battery can be produced as follows.
まずリチウム二次電池に用いる正極は、正極活物質、導電材およびバインダーを含む正極合剤を正極集電体に担持させて製造する。前記導電材としては炭素質材料を用いることができ、炭素質材料として黒鉛粉末、カーボンブラック、アセチレンブラックなどを挙げることができる。カーボンブラックやアセチレンブラックは、微粒で表面積が大きいため、少量正極合剤中に添加することにより正極内部の導電性を高め、充放電効率及びレート特性を向上させることができるが、多く入れすぎるとバインダーによる正極合剤と正極集電体との結着性を低下させ、かえって内部抵抗を増加させる原因となる。通常、正極合剤中の導電材の割合は、５重量％以上２０重量％以下である。 First, a positive electrode used for a lithium secondary battery is manufactured by supporting a positive electrode mixture containing a positive electrode active material, a conductive material, and a binder on a positive electrode current collector. A carbonaceous material can be used as the conductive material, and examples of the carbonaceous material include graphite powder, carbon black, and acetylene black. Since carbon black and acetylene black are fine particles and have a large surface area, adding a small amount to the positive electrode mixture can increase the conductivity inside the positive electrode and improve the charge / discharge efficiency and rate characteristics. This decreases the binding property between the positive electrode mixture and the positive electrode current collector by the binder, and causes an increase in internal resistance. Usually, the proportion of the conductive material in the positive electrode mixture is 5% by weight or more and 20% by weight or less.
前記バインダーとしては、熱可塑性樹脂を用いることができ、具体的には、ポリフッ化ビニリデン（以下、ＰＶＤＦということがある。）、ポリテトラフルオロエチレン（以下、ＰＴＦＥということがある。）、四フッ化エチレン・六フッ化プロピレン・フッ化ビニリデン系共重合体、六フッ化プロピレン・フッ化ビニリデン系共重合体、四フッ化エチレン・パーフルオロビニルエーテル系共重合体などのフッ素樹脂、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂等が挙げられる。また、これらの二種以上を混合して用いてもよい。また、バインダーとしてフッ素樹脂およびポリオレフィン樹脂を用い、正極合剤に対する該フッ素樹脂の割合が１〜１０重量％、該ポリオレフィン樹脂の割合が０．１〜２重量％となるように含有させることによって、正極集電体との結着性に優れた正極合剤を得ることができる。 As the binder, a thermoplastic resin can be used. Specifically, polyvinylidene fluoride (hereinafter sometimes referred to as PVDF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), and four fluorine. Fluoropolymers such as fluorinated ethylene / hexafluoropropylene / vinylidene fluoride copolymers, propylene hexafluoride / vinylidene fluoride copolymers, tetrafluoroethylene / perfluorovinyl ether copolymers, polyethylene, polypropylene, etc. Polyolefin resin and the like. Moreover, you may mix and use these 2 or more types. Further, by using a fluororesin and a polyolefin resin as a binder, the ratio of the fluororesin to the positive electrode mixture is 1 to 10% by weight, and the ratio of the polyolefin resin is 0.1 to 2% by weight, A positive electrode mixture excellent in binding property with the positive electrode current collector can be obtained.
前記正極集電体としては、Ａｌ、Ｎｉ、ステンレスなどを用いることができるが、薄膜に加工しやすく、安価であるという点でＡｌが好ましい。正極集電体に正極合剤を担持させる方法としては、加圧成型する方法、または有機溶媒などを用いてペースト化し、正極集電体上に塗布、乾燥後プレスするなどして固着する方法が挙げられる。ペースト化する場合、正極活物質、導電材、バインダー、有機溶媒からなるスラリーを作製する。有機溶媒としては、Ｎ，Ｎ―ジメチルアミノプロピルアミン、ジエチレントリアミン等のアミン系溶媒、テトラヒドロフラン等のエーテル系溶媒、メチルエチルケトン等のケトン系溶媒、酢酸メチル等のエステル系溶媒、ジメチルアセトアミド、１−メチル−２−ピロリドン等のアミド系溶媒等が挙げられる。 As the positive electrode current collector, Al, Ni, stainless steel or the like can be used, but Al is preferable in that it is easily processed into a thin film and is inexpensive. As a method of supporting the positive electrode mixture on the positive electrode current collector, there is a method of pressure molding, or a method of pasting using an organic solvent or the like, applying onto the positive electrode current collector, drying and pressing to fix the positive electrode current collector. Can be mentioned. In the case of forming a paste, a slurry composed of a positive electrode active material, a conductive material, a binder, and an organic solvent is prepared. Examples of the organic solvent include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine, ether solvents such as tetrahydrofuran, ketone solvents such as methyl ethyl ketone, ester solvents such as methyl acetate, dimethylacetamide, 1-methyl- Examples include amide solvents such as 2-pyrrolidone.
正極合剤を正極集電体へ塗布する方法としては、例えば、スリットダイ塗工法、スクリーン塗工法、カーテン塗工法、ナイフ塗工法、グラビア塗工法、静電スプレー法等が挙げられる。以上に挙げた方法により、非水電解質二次電池用正極を製造することができる。 Examples of the method for applying the positive electrode mixture to the positive electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method. By the method mentioned above, the positive electrode for nonaqueous electrolyte secondary batteries can be manufactured.
上述の正極を用いて、次のようにして、リチウム二次電池を製造することができる。すなわち、セパレータ、負極集電体に負極合剤が担持されてなる負極、および上述の正極を、積層および巻回することにより得られる電極群を、電池缶内に収納した後、電解質を含有する有機溶媒からなる電解液を含浸させて製造することができる。 Using the positive electrode described above, a lithium secondary battery can be produced as follows. That is, a separator, a negative electrode in which a negative electrode mixture is supported on a negative electrode current collector, and an electrode group obtained by laminating and winding the above-described positive electrode are housed in a battery can and then contain an electrolyte. It can be produced by impregnating an electrolytic solution composed of an organic solvent.
前記の電極群の形状としては、例えば、該電極群を巻回の軸と垂直方向に切断したときの断面が、円、楕円、長方形、角がとれたような長方形等となるような形状を挙げることができる。また、電池の形状としては、例えば、ペーパー型、コイン型、円筒型、角型などの形状を挙げることができる。 As the shape of the electrode group, for example, a shape in which the cross section when the electrode group is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, a rectangle with rounded corners, etc. Can be mentioned. In addition, examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
前記負極としては、リチウムイオンをドープ・脱ドーブ可能な材料を含む負極合剤を負極集電体に担持したもの、リチウム金属またはリチウム合金などを用いることができ、リチウムイオンをドープ・脱ドーブ可能な材料としては、具体的には、天然黒鉛、人造黒鉛、コークス類、カーボンブラック、熱分解炭素類、炭素繊維、有機高分子化合物焼成体などの炭素質材料が挙げられ、正極よりも低い電位でリチウムイオンのドープ・脱ドープを行うことができる酸化物、硫化物等のカルコゲン化合物を用いることもできる。炭素質材料としては、電位平坦性が高い点、平均放電電位が低い点などから、天然黒鉛、人造黒鉛等の黒鉛を主成分とする炭素質材料を用いればよい。炭素質材料の形状としては、例えば天然黒鉛のような薄片状、メソカーボンマイクロビーズのような球状、黒鉛化炭素繊維のような繊維状、または微粉末の凝集体などのいずれでもよい。前記の電解液が後述のエチレンカーボネートを含有しない場合において、ポリエチレンカーボネートを含有した負極合剤を用いると、得られる電池のサイクル特性と大電流放電特性が向上することがある。 As the negative electrode, a negative electrode mixture containing a material capable of doping and dedoping lithium ions supported on a negative electrode current collector, lithium metal or lithium alloy, etc. can be used, and lithium ions can be doped and dedoped. Specific examples of such materials include carbonaceous materials such as natural graphite, artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and fired organic polymer compounds, and have a lower potential than the positive electrode. It is also possible to use chalcogen compounds such as oxides and sulfides that can be doped and dedoped with lithium ions. As the carbonaceous material, a carbonaceous material containing graphite as a main component, such as natural graphite or artificial graphite, may be used because of its high potential flatness and low average discharge potential. The shape of the carbonaceous material may be, for example, a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder. In the case where the electrolyte solution does not contain ethylene carbonate described later, when a negative electrode mixture containing polyethylene carbonate is used, the cycle characteristics and large current discharge characteristics of the obtained battery may be improved.
前記の負極合剤は、必要に応じて、バインダーを含有してもよい。バインダーとしては、熱可塑性樹脂を挙げることができ、具体的には、ＰＶＤＦ、熱可塑性ポリイミド、カルボキシメチルセルロース、ポリエチレン、ポリプロピレンなどを挙げることができる。 The negative electrode mixture may contain a binder as necessary. Examples of the binder include a thermoplastic resin, and specific examples include PVDF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene, and polypropylene.
また負極合剤に含有されるリチウムイオンをドープ・脱ドーブ可能な材料として用いられる前記の酸化物、硫化物等のカルコゲン化合物としては、周期率表の１３、１４、１５族の元素を主体とした結晶質または非晶質の酸化物、硫化物等のカルコゲン化合物が挙げられ、具体的には、スズ酸化物を主体とした非晶質化合物等が挙げられる。これらは必要に応じて導電材としての炭素質材料を含有することができる。 The chalcogen compounds such as oxides and sulfides used as a material capable of doping and dedoping lithium ions contained in the negative electrode mixture are mainly composed of elements of Groups 13, 14, and 15 of the periodic table. Examples thereof include chalcogen compounds such as crystalline or amorphous oxides and sulfides, and specific examples include amorphous compounds mainly composed of tin oxide. These can contain a carbonaceous material as a conductive material as required.
前記の負極集電体としては、Ｃｕ、Ｎｉ、ステンレスなどを挙げることができ、リチウムと合金を作り難い点、薄膜に加工しやすいという点で、Ｃｕを用いればよい。該負極集電体に負極合剤を担持させる方法としては、正極の場合と同様であり、加圧成型による方法、溶媒などを用いてペースト化し負極集電体上に塗布、乾燥後プレスし圧着する方法等が挙げられる。 Examples of the negative electrode current collector include Cu, Ni, and stainless steel. Cu may be used because it is difficult to form an alloy with lithium and it is easy to process into a thin film. The method of supporting the negative electrode mixture on the negative electrode current collector is the same as in the case of the positive electrode. The method is a method of pressure molding, pasted using a solvent, etc., coated on the negative electrode current collector, dried, pressed and pressed. And the like.
前記セパレータとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、フッ素樹脂、含窒素芳香族重合体などの材質からなる、多孔質膜、不織布、織布などの形態を有する材料を用いることができ、また、これらの材質を２種以上用いたセパレータとしてもよい。セパレータとしては、例えば特開２０００−３０６８６号公報、特開平１０−３２４７５８号公報等に記載のセパレータを挙げることができる。セパレータの厚みは電池の体積エネルギー密度が上がり、内部抵抗が小さくなるという点で、機械的強度が保たれる限り薄くした方がよく、通常１０〜２００μｍ程度、好ましくは１０〜３０μｍ程度である。 As the separator, for example, a material having a form such as a porous membrane, a nonwoven fabric, a woven fabric made of a polyolefin resin such as polyethylene and polypropylene, a fluororesin, a nitrogen-containing aromatic polymer, and the like can be used. Moreover, it is good also as a separator which used 2 or more types of these materials. Examples of the separator include separators described in JP 2000-30686 A, JP 10-324758 A, and the like. The thickness of the separator is preferably about 10 to 200 μm, and preferably about 10 to 30 μm, as long as the mechanical strength is maintained because the volume energy density of the battery is increased and the internal resistance is reduced.
前記電解液において、電解質としては、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬＩＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＣ（ＳＯ2ＣＦ3）3、Ｌｉ2Ｂ10Ｃｌ10、低級脂肪族カルボン酸リチウム塩、ＬｉＡｌＣｌ4などが挙げられ、これらの２種以上の混合物を使用してもよい。通常、これらの中でもフッ素を含むＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＳＯ2ＣＦ3）2およびＬｉＣ（ＳＯ2ＣＦ3）3からなる群から選ばれた少なくとも１種を含むものを用いる。 In the electrolyte, the electrolyte, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LIBF 4, LiCF 3 SO 3, LiN (SO 2 CF 3) 2, LiC (SO 2 CF 3) 3, Li 2 B 10 Cl 10 , lower aliphatic carboxylic acid lithium salt, LiAlCl 4 and the like can be mentioned, and a mixture of two or more of these may be used. Usually, among these, at least selected from the group consisting of LiPF 6 containing fluorine, LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 and LiC (SO 2 CF 3 ) 3 One containing one kind is used.
また前記電解液において、有機溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、４−トリフルオロメチル−１，３−ジオキソラン−２−オン、１，２−ジ（メトキシカルボニルオキシ）エタンなどのカーボネート類；１，２−ジメトキシエタン、１，３−ジメトキシプロパン、ペンタフルオロプロピルメチルエーテル、２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフランなどのエーテル類；ギ酸メチル、酢酸メチル、γ−ブチロラクトンなどのエステル類；アセトニトリル、ブチロニトリルなどのニトリル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；３−メチル−２−オキサゾリドンなどのカーバメート類；スルホラン、ジメチルスルホキシド、１，３−プロパンサルトンなどの含硫黄化合物、または上記の有機溶媒にさらにフッ素置換基を導入したものを用いることができるが、通常はこれらのうちの二種以上を混合して用いる。中でもカーボネート類を含む混合溶媒が好ましく、環状カーボネートと非環状カーボネート、または環状カーボネートとエーテル類の混合溶媒がさらに好ましい。環状カーボネートと非環状カーボネートの混合溶媒としては、動作温度範囲が広く、負荷特性に優れ、かつ負極の活物質として天然黒鉛、人造黒鉛等の黒鉛材料を用いた場合でも難分解性であるという点で、エチレンカーボネート、ジメチルカーボネートおよびエチルメチルカーボネートを含む混合溶媒が好ましい。また、特に優れた安全性向上効果が得られる点で、ＬｉＰＦ6等のフッ素を含むリチウム塩およびフッ素置換基を有する有機溶媒を含む電解液を用いることが好ましい。ペンタフルオロプロピルメチルエーテル、２，２，３，３−テトラフルオロプロピルジフルオロメチルエーテル等のフッ素置換基を有するエーテル類とジメチルカーボネートとを含む混合溶媒は、大電流放電特性にも優れており、さらに好ましい。 In the electrolytic solution, examples of the organic solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di ( Carbonates such as methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2-methyl Ethers such as tetrahydrofuran; esters such as methyl formate, methyl acetate and γ-butyrolactone; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethylacetate Amides such as amides; Carbamates such as 3-methyl-2-oxazolidone; Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 1,3-propane sultone, or those obtained by further introducing a fluorine substituent into the above organic solvent Usually, two or more of these are mixed and used. Among these, a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or cyclic carbonate and ether is more preferable. The mixed solvent of cyclic carbonate and non-cyclic carbonate has a wide operating temperature range, excellent load characteristics, and is hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material. In addition, a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable. Further, in view of particularly excellent safety improving effect is obtained, it is preferable to use an electrolytic solution containing an organic solvent having a lithium salt and a fluorine substituent containing fluorine such as LiPF 6. A mixed solvent containing ethers having fluorine substituents such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether and dimethyl carbonate has excellent high-current discharge characteristics, preferable.
上記の電解液の代わりに固体電解質を用いてもよい。固体電解質としては、例えばポリエチレンオキサイド系の高分子化合物、ポリオルガノシロキサン鎖もしくはポリオキシアルキレン鎖の少なくとも一種以上を含む高分子化合物などの高分子電解質を用いることができる。また、高分子に非水電解質溶液を保持させた、いわゆるゲルタイプのものを用いることもできる。またＬｉ2Ｓ−ＳｉＳ2、Ｌｉ2Ｓ−ＧｅＳ2、Ｌｉ2Ｓ−Ｐ2Ｓ5、Ｌｉ2Ｓ−Ｂ2Ｓ3などの硫化物電解質、またはＬｉ2Ｓ−ＳｉＳ2−Ｌｉ3ＰＯ4、Ｌｉ2Ｓ−ＳｉＳ2−Ｌｉ2ＳＯ4などの硫化物を含む無機化合物電解質を用いると、安全性をより高めることができることがある。 A solid electrolyte may be used instead of the above electrolytic solution. As the solid electrolyte, for example, a polymer electrolyte such as a polyethylene oxide polymer compound, a polymer compound including at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used. Moreover, what is called a gel type which hold | maintained the nonaqueous electrolyte solution in the polymer | macromolecule can also be used. The Li 2 S-SiS 2, Li 2 S-GeS 2, Li 2 S-P 2 S 5, Li 2 sulfide electrolyte such as S-B 2 S 3, or Li 2 S-SiS 2 -Li 3 PO 4 When an inorganic compound electrolyte containing a sulfide such as Li 2 S—SiS 2 —Li 2 SO 4 is used, safety may be further improved.
次に、本発明を実施例によりさらに詳細に説明する。なお、特に断らない限り、充放電試験用の平板型電池の製造、は下記の方法により行った。 Next, the present invention will be described in more detail with reference to examples. In addition, unless otherwise indicated, the manufacture of a flat battery for a charge / discharge test was performed by the following method.
正極活物質（リチウム複合金属酸化物）と導電材アセチレンブラックの混合物に、バインダーとしてＰＶＤＦの１−メチル−２−ピロリドン（以下、ＮＭＰということがある。）溶液を、活物質：導電材：バインダー＝８６：１０：４（重量比）の組成となるように加えて混練することによりペーストとし、集電体となる＃２００ステンレスメッシュに該ペーストを塗布して１５０℃で８時間真空乾燥を行い、正極を得た。 A mixture of a positive electrode active material (lithium composite metal oxide) and a conductive material acetylene black is mixed with a 1-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP) solution of PVDF as a binder, and the active material: conductive material: binder. = 86: 10: 4 (weight ratio) and then kneaded to obtain a paste. The paste was applied to a # 200 stainless mesh as a current collector and dried in vacuum at 150 ° C. for 8 hours. A positive electrode was obtained.
得られた正極に、電解液としてエチレンカーボネート（以下、ＥＣということがある。）とエチルメチルカーボネート（以下、ＥＭＣということがある。）との５０：５０（体積比）混合液にＬｉＰＦ6を１モル／リットルとなるように溶解したもの（以下、ＬｉＰＦ6／ＥＣ＋ＥＭＣと表すことがある。）、セパレータとしてポリプロピレン多孔質膜を、また、負極として金属リチウムを組み合わせて平板型電池を作製した。 LiPF 6 was added to a 50:50 (volume ratio) mixed solution of ethylene carbonate (hereinafter sometimes referred to as EC) and ethylmethyl carbonate (hereinafter sometimes referred to as EMC) as an electrolytic solution on the obtained positive electrode. A flat battery was prepared by combining a material dissolved to 1 mol / liter (hereinafter sometimes referred to as LiPF 6 / EC + EMC), a polypropylene porous film as a separator, and metallic lithium as a negative electrode.
上記の平板型電池を用いて、６０℃保持下、以下の充放電条件で、定電流定電圧充電、定電流放電による充放電試験を実施した。充放電試験のサイクルを繰り返し、所定回数のサイクルにおける放電容量を測定し、以下に従い、容量維持率を計算した。
＜充放電条件＞
充電最大電圧４．３Ｖ、充電時間８時間、充電電流０．４ｍＡ／ｃｍ2
放電最小電圧３．０Ｖ、放電電流０．４ｍＡ／ｃｍ2
＜容量維持率＞
容量維持率（％）＝所定回数のサイクルにおける放電容量／初回放電容量×１００
Using the above flat battery, a charge / discharge test by constant current / constant voltage charge and constant current discharge was carried out under the following charge / discharge conditions while maintaining at 60 ° C. The cycle of the charge / discharge test was repeated, the discharge capacity in a predetermined number of cycles was measured, and the capacity retention rate was calculated according to the following.
<Charging / discharging conditions>
Charging maximum voltage 4.3V, charging time 8 hours, charging current 0.4mA / cm 2
Discharge minimum voltage 3.0V, discharge current 0.4mA / cm 2
<Capacity maintenance rate>
Capacity maintenance rate (%) = discharge capacity in a predetermined number of cycles / initial discharge capacity × 100
実施例１
１．リチウム複合金属酸化物の製造
チタン製ビーカー内で、水酸化リチウム一水和物５０ｇ、蒸留水５００ｍｌおよびエタノール２００ｍｌを用いて、攪拌し、水酸化リチウム一水和物を完全に溶解させ、水酸化リチウム水溶液を調製した。水酸化リチウム水溶液入りチタン製ビーカーを低温恒温槽内に静置して、−１０℃で保持した。ガラス製ビーカー内で、塩化ニッケル（ＩＩ）六水和物２０．２０ｇ、塩化マンガン（ＩＩ）四水和物２０．７８ｇ、硝酸コバルト（ＩＩ）六水和物１４．５５ｇ（Ｎｉ：Ｍｎ：Ｃｏのモル比は０．３５：０．４４：０．２１である。）および蒸留水５００ｍｌを用いて、攪拌し、上記の塩化ニッケル（ＩＩ）六水和物、塩化マンガン（ＩＩ）四水和物および硝酸コバルト（ＩＩ）六水和物の金属塩を完全に溶解させ、ニッケル−マンガン−コバルト水溶液を得た。該水溶液を、−１０℃に保持した水酸化リチウム水溶液に、滴下し、沈殿を生成させた。
Example 1
1. Production of lithium composite metal oxide In a titanium beaker, 50 g of lithium hydroxide monohydrate, 500 ml of distilled water and 200 ml of ethanol were stirred to completely dissolve the lithium hydroxide monohydrate, and hydroxylated. A lithium aqueous solution was prepared. A titanium beaker containing an aqueous lithium hydroxide solution was placed in a low-temperature thermostatic chamber and kept at -10 ° C. In a glass beaker, 20.20 g of nickel chloride (II) hexahydrate, 20.78 g of manganese chloride (II) tetrahydrate, 14.55 g of cobalt nitrate (II) hexahydrate (Ni: Mn: Co The molar ratio is 0.35: 0.44: 0.21) and 500 ml of distilled water, and the mixture is stirred and mixed with nickel (II) chloride hexahydrate and manganese (II) chloride tetrahydrate. And a metal salt of cobalt nitrate (II) hexahydrate were completely dissolved to obtain a nickel-manganese-cobalt aqueous solution. The aqueous solution was added dropwise to a lithium hydroxide aqueous solution maintained at −10 ° C. to generate a precipitate.
次いで、生成した沈殿を含む混合液を、低温恒温槽から取出し、室温で空気を吹き込む操作（バブリング）を１日行った。バブリング後に得られた混合液について、ろ過・蒸留水洗浄し、沈殿を得た。 Subsequently, the liquid mixture containing the produced | generated precipitation was taken out from the low temperature thermostat, and operation (bubbling) which blows in air at room temperature was performed for 1 day. The mixed solution obtained after bubbling was filtered and washed with distilled water to obtain a precipitate.
ポリテトラフルオロエチレン製ビーカー内で、水酸化リチウム一水和物５０ｇ、塩素酸カリウム５０ｇ、水酸化カリウム３０９ｇおよび蒸留水５００ｍｌを用いて、攪拌し、上記で得た沈殿を添加して、さらに攪拌して沈殿を分散させ、液状混合物を得た。 In a polytetrafluoroethylene beaker, stir with 50 g of lithium hydroxide monohydrate, 50 g of potassium chlorate, 309 g of potassium hydroxide and 500 ml of distilled water, add the precipitate obtained above, and stir further Thus, the precipitate was dispersed to obtain a liquid mixture.
上記の液状混合物入りのポリテトラフルオロエチレン製ビーカーをオートクレーブ中に静置し、２２０℃の温度で５時間水熱処理し、自然冷却し、水熱処理品を得た。水熱処理品をオートクレーブから取出し、蒸留水にてデカンテーションを行って、洗浄品を得た。 The polytetrafluoroethylene beaker containing the liquid mixture was allowed to stand in an autoclave, hydrothermally treated at a temperature of 220 ° C. for 5 hours, and naturally cooled to obtain a hydrothermally treated product. The hydrothermally treated product was taken out from the autoclave and decanted with distilled water to obtain a washed product.
この洗浄品と、水酸化リチウム一水和物１０．４９ｇを蒸留水１００ｍｌに溶解させた水酸化リチウム水溶液とを混合し、１００℃で乾燥させ、混合物を得た。次いで、混合物をメノウ乳鉢を用いて粉砕して得られた粉末をアルミナ製焼成容器に入れ、電気炉を用いて大気中８００℃で焼成を６時間行った。焼成品を室温まで冷却し、粉砕し、蒸留水でデカンテーションによる洗浄を行い、ろ過し、１００℃で８時間乾燥して、粉末Ａ1を得た。 This washed product was mixed with a lithium hydroxide aqueous solution in which 10.49 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water, and dried at 100 ° C. to obtain a mixture. Subsequently, the powder obtained by pulverizing the mixture using an agate mortar was placed in an alumina firing container, and firing was performed in the atmosphere at 800 ° C. for 6 hours using an electric furnace. The calcined product was cooled to room temperature, pulverized, washed with distilled water by decantation, filtered and dried for 8 hours at 100 ° C., to obtain a powder A 1.
２．リチウム二次電池の充放電試験
粉末Ａ1を用いて平板型電池を作製し、充放電試験のサイクルを繰り返した結果、初回、１０回目、２０回目、３０回目、５０回目における放電容量（ｍＡｈ／ｇ）は、それぞれ、１１８、１３５、１５１、１６４、１７５であり、容量維持率（％）は、それぞれ１００、１１４、１２８、１３９、１４８であった。
2. Charge / Discharge Test of Lithium Secondary Battery As a result of producing a flat battery using the powder A 1 and repeating the cycle of the charge / discharge test, the discharge capacity (mAh / second) at the first time, the 10th time, the 20th time, the 30th time and the 50th time g) was 118, 135, 151, 164, and 175, respectively, and the capacity retention rates (%) were 100, 114, 128, 139, and 148, respectively.
実施例２
塩化ニッケル（ＩＩ）六水和物２３．１７ｇ、塩化マンガン（ＩＩ）四水和物２３．２５ｇ、硝酸コバルト（ＩＩ）六水和物７．２８ｇを用いて、Ｎｉ：Ｍｎ：Ｃｏのモル比を０．４１：０．４９：０．１０とした以外は、実施例１と同様にして、粉末Ａ2を得た。
粉末Ａ2を用いて平板型電池を作製し、充放電試験のサイクルを繰り返した結果、初回、１０回目、２０回目、３０回目、５０回目における放電容量（ｍＡｈ／ｇ）は、それぞれ、１１３、１３２、１５４、１６９、１７７であり、容量維持率（％）は、それぞれ１００、１１７、１３６、１４９、１５６であった。
Example 2
Ni: Mn: Co molar ratio using 23.17 g of nickel (II) chloride hexahydrate, 23.25 g of manganese chloride (II) tetrahydrate and 7.28 g of cobalt nitrate (II) hexahydrate. 0.41: 0.49: except for using 0.10, in the same manner as in example 1, to obtain a powder a 2.
As a result of producing a flat battery using the powder A 2 and repeating the cycle of the charge / discharge test, the discharge capacity (mAh / g) at the first, 10th, 20th, 30th and 50th times was 113, 132, 154, 169, and 177, and the capacity retention rates (%) were 100, 117, 136, 149, and 156, respectively.
実施例３
硝酸コバルト（ＩＩ）六水和物を用いずに、塩化ニッケル（ＩＩ）六水和物２６．１５ｇ、塩化マンガン（ＩＩ）四水和物２５．７３ｇを用いて、Ｎｉ：Ｍｎのモル比を０．４６：０．５４とした以外は、実施例１と同様にして、粉末Ａ3を得た。
粉末Ａ3を用いて平板型電池を作製し、充放電試験のサイクルを繰り返した結果、初回、１０回目、２０回目、３０回目、５０回目における放電容量（ｍＡｈ／ｇ）は、それぞれ、１１２、１２７、１４３、１５４、１６３であり、容量維持率（％）は、それぞれ１００、１１３、１２７、１３７、１４５であった。
Example 3
Without using cobalt nitrate (II) hexahydrate, 26.15 g of nickel (II) chloride hexahydrate and 25.73 g of manganese (II) chloride tetrahydrate were used to determine the molar ratio of Ni: Mn. 0.46: except for using 0.54, in the same manner as in example 1 to obtain a powder a 3.
As a result of producing a flat battery using the powder A 3 and repeating the cycle of the charge / discharge test, the discharge capacity (mAh / g) at the first, 10th, 20th, 30th and 50th times was 112, 127, 143, 154, and 163, and capacity retention rates (%) were 100, 113, 127, 137, and 145, respectively.
実施例４
水熱処理の条件を、２２０℃の温度で、４８時間とした以外は、実施例１と同様にして、水熱処理品を得た。この水熱処理品をオートクレーブから取出し、蒸留水にてデカンテーションにより洗浄して、得られる洗浄品をシャーレに移して乾燥し、乾燥品を得た。
Example 4
A hydrothermal treatment product was obtained in the same manner as in Example 1 except that the hydrothermal treatment was performed at a temperature of 220 ° C. for 48 hours. The hydrothermally treated product was taken out from the autoclave, washed with distilled water by decantation, and the resulting washed product was transferred to a petri dish and dried to obtain a dried product.
この乾燥品と、水酸化リチウム一水和物１０．４９ｇを蒸留水１００ｍｌに溶解させた水酸化リチウム水溶液とを混合し、１００℃で乾燥させ、混合物を得た。次いで、混合物をメノウ乳鉢を用いて粉砕して得られた粉末をアルミナ製焼成容器に入れ、電気炉を用いて大気中８００℃で焼成を６時間行った。焼成品を室温まで冷却し、粉砕し、蒸留水でデカンテーションによる洗浄を行い、ろ過し、１００℃で８時間乾燥して、粉末Ａ4を得た。
粉末Ａ4を用いて平板型電池を作製し、充放電試験のサイクルを繰り返した結果、初回、１０回目、２０回目における放電容量（ｍＡｈ／ｇ）は、それぞれ、１０６、１３３、１５９であり、容量維持率（％）は、それぞれ１００、１２６、１５０であった。
This dried product and a lithium hydroxide aqueous solution in which 10.49 g of lithium hydroxide monohydrate was dissolved in 100 ml of distilled water were mixed and dried at 100 ° C. to obtain a mixture. Subsequently, the powder obtained by pulverizing the mixture using an agate mortar was placed in an alumina firing container, and firing was performed in the atmosphere at 800 ° C. for 6 hours using an electric furnace. The calcined product was cooled to room temperature, pulverized, washed with distilled water by decantation, filtered and dried for 8 hours at 100 ° C., to obtain a powder A 4.
As a result of producing a flat battery using the powder A 4 and repeating the cycle of the charge / discharge test, the discharge capacities (mAh / g) at the first, tenth and twentieth times are 106, 133 and 159, respectively. The capacity retention rates (%) were 100, 126, and 150, respectively.
比較例１
１．リチウム複合金属酸化物の製造
水酸化ニッケル（関西触媒化学株式会社製）、酸化マンガン（高純度化学製）、炭酸リチウム（本荘ケミカル株式会社製）、酸化コバルト（正同化学社製）、ホウ酸（米山化学）を各元素のモル比がＬｉ：Ｎｉ：Ｍｎ：Ｃｏ：Ｂ＝１．１５：０．３６：０．４２：０．２１：０．０３とし、粉末の総量１ｋｇとなるように秤取した後、１５ｍｍφのアルミナボール５．７５ｋｇをメディアとした乾式ボールミルにより４時間（容積５Ｌ 周速０．７ｍ／ｓ）粉砕混合し粉体を得た。この粉体を箱型の電気炉に入れ、空気中にて１０４０℃で４時間保持して焼成し、焼成品を得た。該焼成品をプラスチックハンマーにて粗粉砕を行った後、粗粉砕品１ｋｇを１５ｍｍφのアルミナボール５.７５ｋｇをメディアとした乾式ボールミルにより５時間（容積５Ｌ 周速０．７ｍ／ｓ）本粉砕し、粉砕粉末を得た。該粉砕粉末を４５μｍの目開きの篩にて粗粒子を除去し、得られた粉末を、蒸留水でデカンテーションによる洗浄を行い、ろ過し、１００℃で８時間乾燥して、粉末Ｂ1を得た。
Comparative Example 1
1. Manufacture of lithium composite metal oxides Nickel hydroxide (manufactured by Kansai Catalytic Chemical Co., Ltd.), manganese oxide (manufactured by high purity chemical), lithium carbonate (manufactured by Honjo Chemical Co., Ltd.), cobalt oxide (manufactured by Shodo Chemical Co., Ltd.), boric acid (Yoneyama Kagaku) is set so that the molar ratio of each element is Li: Ni: Mn: Co: B = 1.15: 0.36: 0.42: 0.21: 0.03, and the total amount of powder is 1 kg. After weighing, it was pulverized and mixed for 4 hours (volume 5 L, peripheral speed 0.7 m / s) by a dry ball mill using 5.75 kg of 15 mmφ alumina balls as media to obtain powder. This powder was put into a box-type electric furnace and fired in air at 1040 ° C. for 4 hours to obtain a fired product. The fired product is coarsely pulverized with a plastic hammer, and then 1 kg of the coarsely pulverized product is pulverized for 5 hours (volume: 5 L, peripheral speed: 0.7 m / s) by a dry ball mill using 5.75 kg of 15 mmφ alumina balls as media. A pulverized powder was obtained. Coarse particles are removed from the pulverized powder with a sieve having an opening of 45 μm, and the obtained powder is washed by decantation with distilled water, filtered, dried at 100 ° C. for 8 hours, and powder B 1 is obtained. Obtained.
２．リチウム二次電池の充放電試験
粉末Ｂ1を用いて平板型電池を作製し、充放電試験のサイクルを繰り返した結果、初回、１０回目、２０回目における放電容量（ｍＡｈ／ｇ）は、それぞれ、１６４、１５７、１５３であり、容量維持率（％）は、それぞれ１００、９５、９３であった。
2. As a result of producing a flat battery using the powder B 1 and repeating the cycle of the charge / discharge test, the discharge capacity (mAh / g) at the first time, the 10th time, and the 20th time is as follows. 164, 157, and 153, and the capacity retention rates (%) were 100, 95, and 93, respectively.
Claims (9)
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤と、ＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（４）該洗浄品を乾燥し、乾燥品を得る工程。 A method for producing a lithium composite metal oxide containing Li, Ni and M (where M represents Mn and / or Co), comprising the following (1), (2), (3) and ( A method for producing a lithium composite metal oxide comprising the steps 4) in this order.
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent, and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(4) A step of drying the washed product to obtain a dried product.
（５）上記乾燥品を焼成し、焼成品を得る工程。 Furthermore, the manufacturing method of the lithium composite metal oxide of Claim 1 including the process of the following (5).
(5) A step of firing the dried product to obtain a fired product.
（６）上記乾燥品とリチウム塩とを混合して得られる混合物を焼成し、焼成品を得る工程。 Furthermore, the manufacturing method of the lithium composite metal oxide of Claim 1 including the process of the following (6).
(6) The process of baking the mixture obtained by mixing the said dried product and lithium salt, and obtaining a baked product.
（１）ＮｉおよびＭを含有する水溶液とアルカリ（Ａ）とを混合することにより、沈殿を生成させる工程。
（２）該沈殿と酸化剤とＬｉＯＨを含むアルカリ（Ｂ）とを含有する液状混合物を１５０℃〜３５０℃の温度範囲で水熱処理し、水熱処理品を得る工程。
（３）該水熱処理品を洗浄し、洗浄品を得る工程。
（７）該洗浄品とリチウム塩とを混合して得られる混合物を焼成し、焼成品を得る工程。 A method for producing a lithium composite metal oxide containing Li, Ni and M (where M represents Mn and / or Co), comprising the following (1), (2), (3) and ( A method for producing a lithium composite metal oxide, comprising the step of 7).
(1) A step of producing a precipitate by mixing an aqueous solution containing Ni and M and an alkali (A).
(2) A step of hydrothermally treating the liquid mixture containing the precipitate, the oxidizing agent and the alkali (B) containing LiOH in a temperature range of 150 ° C. to 350 ° C. to obtain a hydrothermally treated product.
(3) A step of washing the hydrothermally treated product to obtain a washed product.
(7) A step of firing the mixture obtained by mixing the washed product and the lithium salt to obtain a fired product.
The method for producing a lithium composite metal oxide according to any one of claims 1 to 8, wherein the alkali (B) further contains KOH.
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| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| JP2008041653A (en) * | 2006-07-10 | 2008-02-21 | Sumitomo Chemical Co Ltd | Lithium compound metal oxide |
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| JP2011516384A (en) * | 2008-04-03 | 2011-05-26 | エルジー・ケム・リミテッド | Novel precursors for the production of lithium composite transition metal oxides |
| JP2010108793A (en) * | 2008-10-31 | 2010-05-13 | Idemitsu Kosan Co Ltd | Positive electrode for all-solid lithium secondary battery, and all-solid lithium secondary battery |
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