JP6745742B2 - Method for producing nickel-cobalt-aluminum composite hydroxide particles and method for producing positive electrode active material - Google Patents
Method for producing nickel-cobalt-aluminum composite hydroxide particles and method for producing positive electrode active material Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 56
- -1 nickel-cobalt-aluminum Chemical compound 0.000 title claims description 47
- 239000002131 composite material Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 239000007774 positive electrode material Substances 0.000 title description 11
- 239000007864 aqueous solution Substances 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 17
- 150000001868 cobalt Chemical class 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000243 solution Substances 0.000 description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 10
- 229940044175 cobalt sulfate Drugs 0.000 description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 10
- 229940053662 nickel sulfate Drugs 0.000 description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229940010048 aluminum sulfate Drugs 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、ニッケルコバルトアルミニウム複合水酸化物粒子の製造方法及び正極活物質の製造方法に関する。 The present invention relates to a method for producing nickel-cobalt-aluminum composite hydroxide particles and a method for producing a positive electrode active material.
リチウムイオン二次電池の正極活物質には、一般にリチウム含有遷移金属複合酸化物が用いられている。具体的には、リチウムイオン二次電池の正極活物質としては、リチウムコバルト複合酸化物とともにリチウムニッケル複合酸化物等が挙げられ、特性改善（高容量化、サイクル特性、保存特性、内部抵抗低減、レート特性）や安全性を高めるためにこれらを複合化することが進められている。 A lithium-containing transition metal composite oxide is generally used as a positive electrode active material of a lithium ion secondary battery. Specifically, examples of the positive electrode active material of a lithium-ion secondary battery include a lithium cobalt composite oxide as well as a lithium nickel composite oxide, which improves characteristics (higher capacity, cycle characteristics, storage characteristics, internal resistance reduction, In order to improve rate characteristics) and safety, compounding these is being promoted.
リチウムイオン二次電池の正極活物質は、通常、リチウム化合物と遷移金属化合物を混合焼成して製造されている。しかしながら、純粋な遷移金属化合物から合成した純粋なリチウム遷移金属複合酸化物では、安全性、サイクル特性等に問題があり、実用電池として使用することが困難であった。 The positive electrode active material of a lithium ion secondary battery is usually manufactured by mixing and firing a lithium compound and a transition metal compound. However, a pure lithium transition metal composite oxide synthesized from a pure transition metal compound has problems in safety, cycle characteristics, etc., and it is difficult to use it as a practical battery.
このような問題に対し、例えば、特許文献１には、次の一般式（１）：
Ｎｉ(1-x-y)ＭxＡｌy（ＯＨ）2 （１）
（式中、Ｍは、Ｃｏ又はＭｎから選ばれる少なくとも１種の元素を示し、ｘは、０．０１〜０．２、及び、ｙは、０．０１〜０．１５である。）
で表されるアルミニウム含有水酸化ニッケル粒子を製造する方法であって、ＮｉとＭ元素を含む金属化合物の水溶液、アルミン酸ナトリウム水溶液、水酸化ナトリウム水溶液、及びアンモニウムイオン供給体を含む水溶液を、それぞれ同一の反応槽内に個別にかつ同時に供給して反応させることを特徴とするアルミニウム含有水酸化ニッケル粒子の製造方法が開示されている。そして、このような構成によれば、錯形成剤やハロゲンなどの混入がなく、リチウムイオン電池正極材料の原料として好適な高密度の球状のアルミニウム含有水酸化ニッケル粒子とその工業的に効率的な製造方法を提供することができると記載されている。
For such a problem, for example, in Patent Document 1, the following general formula (1):
Ni (1-xy) M x Al y (OH) 2 (1)
(In the formula, M represents at least one element selected from Co or Mn, x is 0.01 to 0.2, and y is 0.01 to 0.15.)
A method for producing aluminum-containing nickel hydroxide particles represented by the following, wherein an aqueous solution of a metal compound containing Ni and an M element, an aqueous solution of sodium aluminate, an aqueous solution of sodium hydroxide, and an aqueous solution containing an ammonium ion supplier are respectively prepared. Disclosed is a method for producing aluminum-containing nickel hydroxide particles, which comprises individually and simultaneously supplying and reacting in the same reaction tank. According to such a configuration, a high density spherical aluminum-containing nickel hydroxide particles suitable for a raw material of a lithium ion battery positive electrode material and an industrially efficient mixture-free agent such as a complexing agent and a halogen are not mixed. It is stated that a manufacturing method can be provided.
しかしながら、特許文献１では、ニッケルとＭ元素を含む金属化合物の水溶液は個別に、アルミニウム源としてアルミン酸ナトリウム水溶液を用いているが、このアルミン酸ナトリウム水溶液は、徐々に大気中の二酸化炭素と反応して水酸化アルミニウムを析出してしまうため、水溶液の濃度変化及び反応液の供給ポンプの詰まりなどが生じる。また、アルミン酸ナトリウムに置き換えて、硫酸アルミニウムや硝酸アルミニウムを用いることが考えられるが、ニッケルとＭ元素に加えてアルミニウムを含む金属塩の混合水溶液では、混合水溶液内で水酸化アルミニウムの微粒子が析出してしまうため、反応を行っても小さな粒子しか得られないという問題があった。 However, in Patent Document 1, an aqueous solution of a metal compound containing nickel and an M element is individually used as an aluminum source as an aqueous solution of sodium aluminate, but this aqueous solution of sodium aluminate gradually reacts with carbon dioxide in the atmosphere. As a result, aluminum hydroxide is deposited, resulting in changes in the concentration of the aqueous solution and clogging of the reaction solution supply pump. Further, it is conceivable to use aluminum sulfate or aluminum nitrate in place of sodium aluminate, but in a mixed aqueous solution of a metal salt containing aluminum in addition to nickel and M element, fine particles of aluminum hydroxide are precipitated in the mixed aqueous solution. Therefore, there is a problem that only small particles can be obtained even if the reaction is performed.
このような問題を鑑みて、本発明は、所定の粒径の水酸化物粒子を安定して、すなわち長時間経過しても水溶液の濃度変化及び反応液の供給ポンプの詰まりをさせずに製造することが可能なニッケルコバルトアルミニウム複合水酸化物粒子の製造方法を提供することを課題とする。 In view of such a problem, the present invention can produce hydroxide particles having a predetermined particle size stably, that is, without changing the concentration of an aqueous solution and clogging of a reaction solution supply pump even after a long time. An object of the present invention is to provide a method for producing nickel-cobalt-aluminum composite hydroxide particles that can be manufactured.
本発明は一側面において、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．１≦ｘ＜０．２０、０≦ｙ＜０．１、０．８２≦１−ｘ−ｙ≦０．９、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表される水酸化物粒子の製造方法であって、ニッケル塩及びコバルト塩を含む水溶液、硫酸アルミニウムまたは硝酸アルミニウム水溶液、アルカリ金属水酸化物水溶液、及び、アンモニウムイオンを含む水溶液をそれぞれ個別に反応槽に供給して反応させる工程を含むニッケルコバルトアルミニウム複合水酸化物粒子の製造方法である。
The present invention in one aspect, a composition formula Ni 1-xy Co x M y Al z (OH) 2 + α
(In the formula, 0.1≦ x<0.20 , 0≦y<0.1, 0.82≦1-x−y≦0.9, 0<z<0.05 , 0≦α≦1, M is Mn or Zr), which is a method for producing hydroxide particles, comprising an aqueous solution containing a nickel salt and a cobalt salt, an aluminum sulfate or aluminum nitrate aqueous solution, an alkali metal hydroxide aqueous solution, and ammonium. It is a method for producing nickel-cobalt-aluminum composite hydroxide particles, which includes a step of individually supplying an aqueous solution containing ions to a reaction tank to cause a reaction.
本発明は別の一側面において、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表される水酸化物粒子の製造方法であって、ニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加えて、ｐＨ３．０以下に調製した後、前記混合溶液とアルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ個別に反応槽に供給して反応させる工程を含むニッケルコバルトアルミニウム複合水酸化物粒子の製造方法である。
The present invention in another aspect, a composition formula Ni 1-xy Co x M y Al z (OH) 2 + α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, M is Mn or Zr). a manufacturing method of the oxide particles, the mixed solution of nickel salt and cobalt salt, the addition of aluminum sulfate or aluminum nitrate, after preparation to pH3.0 or less, the mixed solution and an alkali metal hydroxide solution A method for producing nickel-cobalt-aluminum composite hydroxide particles, which comprises the steps of separately supplying an aqueous solution containing ammonium ion and a reaction solution to a reaction tank to cause a reaction.
本発明の水酸化物粒子の製造方法は一実施形態において、前記ｐＨの調整を、ｐＨ２．５〜３．０とする。 In one embodiment of the method for producing hydroxide particles of the present invention, the pH is adjusted to pH 2.5 to 3.0.
本発明の水酸化物粒子の製造方法は別の一実施形態において、前記水酸化物粒子の平均粒径（Ｄ５０）が１０〜２５μｍである。 In another embodiment of the method for producing hydroxide particles of the present invention, the hydroxide particles have an average particle diameter (D50) of 10 to 25 µm.
本発明は更に別の一側面において、本発明のニッケルコバルトアルミニウム複合水酸化物粒子の製造方法で製造された水酸化物粒子を前駆体として、Ｌｉ源と混合した後、焼成する工程を有する正極活物質の製造方法である。 In yet another aspect of the present invention, a positive electrode having a step of mixing the hydroxide particles produced by the method for producing nickel-cobalt-aluminum composite hydroxide particles of the present invention as a precursor with a Li source and then firing the mixture. It is a method for producing an active material.
本発明によれば、所定の粒径の水酸化物粒子を安定して製造することが可能なニッケルコバルトアルミニウム複合水酸化物粒子の製造方法を提供することができる。 According to the present invention, it is possible to provide a method for producing nickel-cobalt-aluminum composite hydroxide particles capable of stably producing hydroxide particles having a predetermined particle size.
（水酸化物粒子の製造方法）
本発明のニッケルコバルトアルミニウム複合水酸化物粒子の製造方法は一側面において、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表されるニッケルコバルトアルミニウム複合水酸化物粒子の製造方法である。
(Method for producing hydroxide particles)
Method for producing a nickel-cobalt-aluminum composite hydroxide particles of the present invention in one aspect, Ni 1-xy Co composition formula of x M y Al z (OH) 2 + α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, and M is Mn or Zr). It is a method for producing cobalt aluminum composite hydroxide particles.
まず、ニッケル塩及びコバルト塩を含む水溶液、硫酸アルミニウムまたは硝酸アルミニウム水溶液、アルカリ金属水酸化物水溶液、及び、アンモニウムイオンを含む水溶液をそれぞれ準備する。 First, an aqueous solution containing nickel salt and cobalt salt, an aqueous solution of aluminum sulfate or aluminum nitrate, an aqueous solution of alkali metal hydroxide, and an aqueous solution containing ammonium ion are prepared.
ニッケル塩及びコバルト塩を含む水溶液としては、硫酸塩、硝酸塩、酢酸塩、塩化物等の水溶液を用いることができる。 As the aqueous solution containing nickel salt and cobalt salt, an aqueous solution of sulfate, nitrate, acetate, chloride and the like can be used.
アルカリ金属水酸化物水溶液としては、水酸化ナトリウム、水酸化カリウム等を用いることができる。アルカリ金属水酸化物水溶液は、反応槽内のｐＨをアルカリ性にし、酸性の硫酸Ｎｉや硫酸Ｃｏや硫酸Ａｌなどを水酸化物として析出させるために使用する。 As the alkali metal hydroxide aqueous solution, sodium hydroxide, potassium hydroxide or the like can be used. The aqueous solution of alkali metal hydroxide is used to make the pH in the reaction vessel alkaline and to precipitate acidic Ni sulfate, Co sulfate, Al sulfate, etc. as hydroxides.
アンモニウムイオンを含む水溶液としては、アンモニア水、硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウム等の水溶液を用いることができる。 As the aqueous solution containing ammonium ions, an aqueous solution of ammonia water, ammonium sulfate, ammonium chloride, ammonium nitrate or the like can be used.
次に、ニッケル塩及びコバルト塩を含む水溶液、硫酸アルミニウムまたは硝酸アルミニウム水溶液、アルカリ金属水酸化物水溶液、及び、アンモニウムイオンを含む水溶液をそれぞれ、個別に同じ反応槽に供給して反応させることで、ニッケルコバルトアルミニウム複合水酸化物粒子を製造する。 Next, an aqueous solution containing a nickel salt and a cobalt salt, an aqueous solution of aluminum sulfate or aluminum nitrate, an aqueous solution of an alkali metal hydroxide, and an aqueous solution containing an ammonium ion are separately supplied to the same reaction tank and reacted, A nickel-cobalt-aluminum composite hydroxide particle is manufactured.
従来、ニッケルコバルトアルミニウム複合水酸化物粒子を作製する際、アルミニウム源としてアルミン酸ナトリウムが用いられていた。しかしながら、アルミン酸ナトリウムは大気中の二酸化炭素と反応し、徐々にアルミニウム源となる水溶液中で水酸化アルミニウムを生じる。そのため、水溶液中のアルミニウムイオン濃度の低下による組成ずれや析出によるポンプのつまり等の問題が生じていた。また、このような水酸化アルミニウムが存在する水溶液を反応槽に添加すると、その微粒子が核となり多くの共沈水酸化物が生じる。これらが増加すると粒子一つ一つの成長量が少なくなるため、結果として得られる粒子が小さくなってしまう。これに対し、本発明では、アルミニウム源として、硫酸アルミニウムまたは硝酸アルミニウムを用いる。すなわち、ニッケル塩及びコバルト塩を含む水溶液、硫酸アルミニウムまたは硝酸アルミニウム水溶液、アルカリ金属水酸化物水溶液、及び、アンモニウムイオンを含む水溶液をそれぞれ、個別に同じ反応槽に供給してニッケルコバルトアルミニウム複合水酸化物を生成する反応を行う。これにより、アルミニウム源となる水溶液中ではなく、反応槽内で水酸化アルミニウムが生成するため、粒子の核になる反応と、反応槽内に存在する粒子の外周部に析出して粒子を成長させる反応が起こる。このように、ニッケルコバルトアルミニウム複合水酸化物の成長阻害要因が無くなり、安定してニッケルコバルトアルミニウム複合水酸化物を成長させることができる。この結果、所定の粒径、例えば平均粒径（Ｄ５０）が１０〜２５μｍであるニッケルコバルトアルミニウム複合水酸化物粒子を安定して、すなわち長時間経過しても水溶液の濃度変化及び反応液の供給ポンプの詰まりをさせずに製造することが可能となる。 Conventionally, sodium aluminate has been used as an aluminum source when producing nickel-cobalt-aluminum composite hydroxide particles. However, sodium aluminate reacts with carbon dioxide in the atmosphere, and gradually produces aluminum hydroxide in an aqueous solution serving as an aluminum source. Therefore, problems such as composition shift due to a decrease in aluminum ion concentration in the aqueous solution and pump clogging due to precipitation have occurred. When an aqueous solution containing such aluminum hydroxide is added to the reaction tank, the fine particles become nuclei and many coprecipitated hydroxides are produced. If they increase, the growth amount of each particle decreases, and the resulting particles become smaller. On the other hand, in the present invention, aluminum sulfate or aluminum nitrate is used as the aluminum source. That is, an aqueous solution containing a nickel salt and a cobalt salt, an aqueous solution of aluminum sulfate or aluminum nitrate, an aqueous solution of an alkali metal hydroxide, and an aqueous solution containing ammonium ions are individually supplied to the same reaction tank to supply nickel cobalt aluminum composite hydroxide. Perform a reaction that produces a product. As a result, aluminum hydroxide is produced in the reaction tank, not in the aqueous solution serving as the aluminum source, so that the reaction becomes a nucleus of the particles and the particles are deposited on the outer periphery of the particles existing in the reaction tank to grow the particles. The reaction takes place. In this way, the growth inhibiting factor of the nickel-cobalt-aluminum composite hydroxide is eliminated, and the nickel-cobalt-aluminum composite hydroxide can be stably grown. As a result, the nickel-cobalt-aluminum composite hydroxide particles having a predetermined particle size, for example, an average particle size (D50) of 10 to 25 μm are stabilized, that is, the concentration change of the aqueous solution and the supply of the reaction solution even after a long time has elapsed. It is possible to manufacture without blocking the pump.
反応槽の反応液のｐＨは９．０〜１３．０であることが好ましく、１０．５〜１２．０であることがより好ましい。また、反応槽の反応液の温度は３０〜７０℃であることが好ましく、４５〜５５℃であることがより好ましい。
図１に上述の本発明の実施形態に係る水酸化物粒子の製造方法の例に係る模式図を示す。
The pH of the reaction solution in the reaction tank is preferably 9.0 to 13.0, more preferably 10.5-12.0. The temperature of the reaction liquid in the reaction tank is preferably 30 to 70°C, more preferably 45 to 55°C.
FIG. 1 shows a schematic diagram relating to an example of the method for producing hydroxide particles according to the embodiment of the present invention.
しかしながら、上記の製法において、硫酸ニッケル、硫酸コバルト、及び、硫酸アルミニウム（もしくは硝酸アルミニウム）を一緒に溶解する場合は、ニッケルコバルトアルミニウム複合水酸化物の成長を阻害してしまう因子である水酸化アルミニウムが水溶液中に生成する。水酸化アルミニウムが生成してしまうと、その後の反応によるニッケルコバルトアルミニウム複合水酸化物の成長が不安定になり、結果として得られる粒子が小さくなってしまう。そのため例えば平均粒径（Ｄ５０）が１０〜２５μｍであるニッケルコバルトアルミニウム複合水酸化物粒子を安定して製造することが難しくなる。従って、硫酸ニッケル、硫酸コバルト、及び、硫酸アルミニウム（もしくは硝酸アルミニウム）を一緒に溶解する場合は、本発明の別の一側面において、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表される水酸化物粒子の製造方法であって、ｐＨ３．０以下のニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加えた後、前記混合溶液とアルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ個別に反応槽に供給して反応させる工程を含むニッケルコバルトアルミニウム複合水酸化物粒子の製造方法である。
However, in the above manufacturing method, when nickel sulfate, cobalt sulfate, and aluminum sulfate (or aluminum nitrate) are dissolved together, aluminum hydroxide which is a factor that inhibits the growth of nickel-cobalt-aluminum composite hydroxide Are produced in the aqueous solution. If aluminum hydroxide is produced, the growth of the nickel-cobalt-aluminum composite hydroxide due to the subsequent reaction becomes unstable, and the resulting particles become small. Therefore, for example, it becomes difficult to stably produce nickel-cobalt-aluminum composite hydroxide particles having an average particle diameter (D50) of 10 to 25 μm. Therefore, nickel sulfate, cobalt sulfate, and, if dissolved together aluminum sulfate (or aluminum nitrate), in another aspect of the present invention, composition formula Ni 1-xy Co x M y Al z (OH) 2+α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, M is Mn or Zr). A method for producing oxide particles, comprising adding aluminum sulfate or aluminum nitrate to a mixed solution of a nickel salt and a cobalt salt having a pH of 3.0 or less, and then including the mixed solution, an alkali metal hydroxide aqueous solution and ammonium ions. It is a method for producing nickel-cobalt-aluminum composite hydroxide particles, which includes a step of individually supplying an aqueous solution to a reaction tank to cause a reaction.
まず、ニッケル塩、コバルト塩、及び濃硫酸等の酸を混合することで、ｐＨ３．０以下のニッケル塩及びコバルト塩の混合溶液を調整する。次に、ｐＨ３．０以下のニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加える。一方、アルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ準備する。 First, a mixed solution of nickel salt and cobalt salt having a pH of 3.0 or less is prepared by mixing nickel salt, cobalt salt, and acid such as concentrated sulfuric acid. Next, aluminum sulfate or aluminum nitrate is added to a mixed solution of nickel salt and cobalt salt having a pH of 3.0 or less. On the other hand, an aqueous alkali metal hydroxide solution and an aqueous solution containing ammonium ions are prepared.
次に、ｐＨ３．０以下のニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加えて作製した混合液とアルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ個別に同じ反応槽に供給して反応させることで、ニッケルコバルトアルミニウム複合水酸化物粒子を製造する。 Next, a mixed solution prepared by adding aluminum sulfate or aluminum nitrate to a mixed solution of nickel salt and cobalt salt having a pH of 3.0 or less, an alkali metal hydroxide aqueous solution, and an aqueous solution containing ammonium ion are individually subjected to the same reaction. The nickel-cobalt-aluminum composite hydroxide particles are produced by supplying them to a tank and reacting them.
ニッケル塩及びコバルト塩を含む水溶液としては、硫酸塩、硝酸塩、酢酸塩、塩化物等の水溶液を用いることができる。 As the aqueous solution containing nickel salt and cobalt salt, an aqueous solution of sulfate, nitrate, acetate, chloride and the like can be used.
アルカリ金属水酸化物水溶液としては、水酸化ナトリウム、水酸化カリウム等を用いることができる。 As the alkali metal hydroxide aqueous solution, sodium hydroxide, potassium hydroxide or the like can be used.
アンモニウムイオンを含む水溶液としては、アンモニア水、硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウム等の水溶液を用いることができる。 As the aqueous solution containing ammonium ions, an aqueous solution of ammonia water, ammonium sulfate, ammonium chloride, ammonium nitrate or the like can be used.
本発明では、ニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加えて溶解させるときに、当該溶液のｐＨを３．０以下に下げておくことにより水酸化アルミニウムの生成がなくなる。それに続いて、当該混合液とアルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ個別に同じ反応槽に供給して反応させる。このためニッケルコバルトアルミニウム複合水酸化物の成長阻害要因が無くなり、安定してニッケルコバルトアルミニウム複合水酸化物を成長させることができる。この結果、所定の粒径、例えば平均粒径（Ｄ５０）が１０〜２５μｍであるニッケルコバルトアルミニウム複合水酸化物粒子を安定して製造することが可能となる。ニッケル塩及びコバルト塩の混合溶液のｐＨは２．５〜３．０であるのが好ましい。 In the present invention, when aluminum sulfate or aluminum nitrate is added to a mixed solution of a nickel salt and a cobalt salt and dissolved therein, the pH of the solution is lowered to 3.0 or less so that aluminum hydroxide is not produced. Subsequently, the mixed solution, the alkali metal hydroxide aqueous solution, and the aqueous solution containing ammonium ions are individually supplied to the same reaction tank to react. Therefore, the growth inhibiting factor of the nickel-cobalt-aluminum composite hydroxide is eliminated, and the nickel-cobalt-aluminum composite hydroxide can be stably grown. As a result, it becomes possible to stably produce nickel-cobalt-aluminum composite hydroxide particles having a predetermined particle diameter, for example, an average particle diameter (D50) of 10 to 25 μm. The pH of the mixed solution of nickel salt and cobalt salt is preferably 2.5 to 3.0.
反応槽の反応液のｐＨは９．０〜１３．０であることが好ましく、１０．５〜１２．０であることがより好ましい。また、反応槽の反応液の温度は３０〜７０℃であることが好ましく、４５〜５５℃であることがより好ましい。
図２に上述の本発明の別の実施形態に係る水酸化物粒子の製造方法の例に係る模式図を示す。
The pH of the reaction solution in the reaction tank is preferably 9.0 to 13.0, more preferably 10.5-12.0. The temperature of the reaction liquid in the reaction tank is preferably 30 to 70°C, more preferably 45 to 55°C.
FIG. 2 shows a schematic diagram relating to an example of the method for producing hydroxide particles according to another embodiment of the present invention described above.
（リチウムイオン二次電池用正極活物質の製造方法）
次に、本発明のリチウムイオン二次電池用正極活物質の製造方法について詳細に説明する。
まず、上述の製造方法によって作製した本発明のニッケルコバルトアルミニウム複合水酸化物粒子を前駆体として、当該前駆体とリチウム源（例えば、水酸化リチウム等）とを混合した後、焼成する。当該混合条件は、例えばリチウム源からのＬｉとニッケルコバルトアルミニウム複合水酸化物粒子からの金属Ｍｅ（Ｎｉ＋Ｃｏ＋Ａｌ）とが、組成比でＬｉ／Ｍｅ（Ｎｉ＋Ｃｏ＋Ａｌ）＝１．００〜１．０５となるように混合する。また、焼成条件は、例えば、４５０〜５２０℃で２〜１５時間焼成した後、さらに７００〜８００℃で２〜１５時間焼成することができる。
(The manufacturing method of the positive electrode active material for lithium ion secondary batteries)
Next, the method for producing the positive electrode active material for a lithium ion secondary battery of the present invention will be described in detail.
First, using the nickel-cobalt-aluminum composite hydroxide particles of the present invention produced by the above-mentioned production method as a precursor, the precursor and a lithium source (for example, lithium hydroxide) are mixed and then fired. The mixing conditions are such that, for example, Li from the lithium source and metal Me(Ni+Co+Al) from the nickel-cobalt-aluminum composite hydroxide particles have a composition ratio of Li/Me(Ni+Co+Al)=1.00 to 1.05. To mix. As for the firing conditions, for example, after firing at 450 to 520° C. for 2 to 15 hours, firing at 700 to 800° C. for 2 to 15 hours can be performed.
次に、焼成した粉(焼成粉)を、必要であれば、ロールミル、パルべライザー等を用いて解砕し、所定の平均粒子径を有する正極活物質を得る。 Next, if necessary, the calcined powder (calcined powder) is crushed using a roll mill, a pulsarizer or the like to obtain a positive electrode active material having a predetermined average particle diameter.
このようにして作製された正極活物質は、特に限定されないが、例えば、以下の組成式で示すことができる。
ＬｉmＮｉ1-x-yＣｏxＭyＡｌz（Ｏ）2+α（式中、０．９５≦ｍ≦１．０５、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）。
The positive electrode active material thus produced is not particularly limited, but can be represented by the following composition formula, for example.
Li m Ni 1-xy Co x M y Al z (O) 2 + α ( wherein, 0.95 ≦ m ≦ 1.05,0.05 <x <0.20,0 ≦ y <0.1, 0<z<0.05, 0≦α≦1, M is Mn or Zr.).
リチウムイオン二次電池用正極は、例えば、上述のリチウムイオン二次電池用正極活物質と、導電助剤と、バインダーとを混合して調製した正極合剤をアルミニウム箔等からなる集電体の片面または両面に設けた構造を有している。正極中には、さらにジ（ビス（６−ｔ−ブチル−４−メチルフェノキシ））チタンなどを添加することもできる。また、本発明のリチウムイオン二次電池は、このような構成のリチウムイオン二次電池用正極と、負極と、電解液とを備えている。 The positive electrode for a lithium ion secondary battery is, for example, a positive electrode mixture prepared by mixing the above-mentioned positive electrode active material for a lithium ion secondary battery, a conductive auxiliary agent, and a binder with a collector made of an aluminum foil or the like. It has a structure provided on one side or both sides. Di(bis(6-t-butyl-4-methylphenoxy))titanium and the like can be further added to the positive electrode. The lithium-ion secondary battery of the present invention includes the positive electrode for a lithium-ion secondary battery having such a structure, a negative electrode, and an electrolytic solution.
以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。 Examples are provided below for better understanding of the present invention and its advantages, but the present invention is not limited to these examples.
（実施例１）
Ｎｉ：Ｃｏのモル比が８２：１５であって金属イオン濃度が１．５ｍｏｌ／Ｌの硫酸ニッケルおよび硫酸コバルトの混合溶液、アルミニウムイオン濃度が０．５ｍｏｌ／Ｌの硫酸アルミニウム水溶液、アンモニウムイオン濃度が４ｍｏｌ／Ｌのアンモニア水、および２０ｗｔ％の水酸化ナトリウム水溶液を調整した。
次に、オーバーフロー口までの容量が１０Ｌである反応槽に１０Ｌの水を張り、反応槽内の温度を５０℃に制御しつつ撹拌を行った。これに上記ニッケルおよびコバルトの混合硫酸塩水溶液を０．７４Ｌ／ｈ、硫酸アルミニウム水溶液を０．０７Ｌ／ｈ、アンモニア水を０．３Ｌ／ｈで供給しつつ、ｐＨ１１．３となるように水酸化ナトリウム水溶液を供給した。このとき、適宜、各槽内の溶液重量を測定し流量を調節した。
次に、４８時間後にオーバーフローしてきた試料を回収し、濾過および水洗を行い、１２０℃で一晩乾燥させたところ、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表されるニッケルコバルトアルミニウム複合水酸化物粒子が得られた。
(Example 1)
A Ni:Co molar ratio of 82:15 and a metal ion concentration of 1.5 mol/L, a mixed solution of nickel sulfate and cobalt sulfate, an aluminum ion concentration of 0.5 mol/L, an aluminum sulfate aqueous solution, and an ammonium ion concentration of 4 mol/L ammonia water and 20 wt% sodium hydroxide aqueous solution were prepared.
Next, 10 L of water was poured into a reaction tank having a capacity up to the overflow port of 10 L, and stirring was performed while controlling the temperature in the reaction tank to 50°C. While supplying 0.74 L/h of the above mixed sulfate aqueous solution of nickel and cobalt, 0.07 L/h of the aluminum sulfate aqueous solution, and 0.3 L/h of aqueous ammonia, hydroxylation was performed so that the pH became 11.3. An aqueous solution of sodium was supplied. At this time, the weight of the solution in each tank was appropriately measured and the flow rate was adjusted.
Next, a sample that has overflowed after 48 hours was collected, followed by filtration and water washing, was dried overnight at 120 ° C., composition formula Ni 1-xy Co x M y Al z (OH) 2 + α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, and M is Mn or Zr). Cobalt-aluminum composite hydroxide particles were obtained.
（参考例２）
実施例１のＮｉ：Ｃｏのモル比を８０：１５としたこと、硫酸アルミニウムに変えて、硝酸アルミニウムとし、流量を０．１２Ｌ／ｈとしたこと、および、アンモニア水の流量を０．６Ｌ／ｈとしたこと以外は実施例１と同じ条件とした。
( Reference example 2)
In Example 1, the molar ratio of Ni:Co was 80:15, aluminum sulfate was changed to aluminum nitrate, the flow rate was 0.12 L/h, and the flow rate of aqueous ammonia was 0.6 L/h. The conditions were the same as in Example 1 except that h was used.
（参考例３）
実施例１のＮｉ：Ｃｏのモル比を９０：５としたこと、硫酸アルミニウムの流量を０．１２Ｌ／ｈとしたこと、アンモニア水に変えて、硫酸アンモニウム水溶液とし、反応槽内への供給を０．２Ｌ／ｈとしたこと、および、ｐＨを１０．８としたこと以外は実施例１と同じ条件とした。
( Reference example 3)
In Example 1, the molar ratio of Ni:Co was set to 90:5, the flow rate of aluminum sulfate was set to 0.12 L/h, ammonia water was replaced with ammonium sulfate aqueous solution, and the supply into the reaction vessel was 0. The conditions were the same as in Example 1 except that the pH was set to 0.2 L/h and the pH was set to 10.8.
（参考例４）
実施例１のＮｉ：Ｃｏのモル比を８０：１９としたこと、硫酸ニッケル、硫酸コバルト、硫酸アルミニウムに変えて、硝酸ニッケル、硝酸コバルト、硝酸アルミニウムとし、硝酸アルミニウムの流量を０．０２Ｌ／ｈとしたこと、アンモニア水の流量を０．６Ｌ／ｈとしたこと、および、ｐＨを１０．８としたこと以外は実施例１と同じ条件とした。
( Reference example 4)
In Example 1, the molar ratio of Ni:Co was set to 80:19, nickel sulfate, cobalt sulfate, and aluminum sulfate were replaced with nickel nitrate, cobalt nitrate, and aluminum nitrate, and the flow rate of aluminum nitrate was 0.02 L/h. The conditions were the same as in Example 1 except that the flow rate of the ammonia water was 0.6 L/h, and the pH was 10.8.
（参考例５）
実施例１の硫酸ニッケルおよび硫酸コバルトの混合溶液に変えて、硫酸ニッケル、硫酸コバルトおよび硫酸マンガンの混合水溶液としＮｉ：Ｃｏ：Ｍｎのモル比を８０：１０：７としたこと、アンモニア水流量を０．６Ｌ／ｈとしたこと、および、ｐＨを１１．８としたこと以外は実施例１と同じ条件とした。
( Reference example 5)
Instead of the mixed solution of nickel sulfate and cobalt sulfate of Example 1, a mixed aqueous solution of nickel sulfate, cobalt sulfate and manganese sulfate was used, and the molar ratio of Ni:Co:Mn was set to 80:10:7. The conditions were the same as in Example 1 except that the pH was 0.6 L/h and the pH was 11.8.
（実施例６）
実施例１の反応槽に供給する水溶液に、ジルコニウムイオン濃度が０．６ｍｏｌ／Ｌの硫酸ジルコニウム水溶液を加え、硫酸ジルコニウム水溶液の供給量を０．０７Ｌ／ｈとした以外は、実施例１と同じ条件とした。
(Example 6)
Same as Example 1 except that an aqueous zirconium sulfate solution having a zirconium ion concentration of 0.6 mol/L was added to the aqueous solution supplied to the reaction tank of Example 1 to make the supply amount of the aqueous zirconium sulfate solution 0.07 L/h. It was a condition.
（実施例７）
Ｎｉ：Ｃｏ：Ａｌのモル比が８２：１５：３であって金属イオン濃度が１．５ｍｏｌ／Ｌの硫酸ニッケル、硫酸コバルトおよび硫酸アルミニウムの混合溶液、アンモニウムイオン濃度が４ｍｏｌ／Ｌのアンモニア水、および２０ｗｔ％の水酸化ナトリウム水溶液を調整した。硫酸ニッケル、硫酸コバルトおよび硫酸アルミニウムの混合溶液は濃硫酸を加え、ｐＨが３．０となるようにした。
次に、オーバーフロー口までの容量が１０Ｌである反応槽に１０Ｌの水を張り、反応槽内の温度を５０℃に制御しつつ撹拌を行った。これに上記ニッケルおよびコバルトの混合硫酸塩水溶液を０．７６Ｌ／ｈ、アンモニア水を０．３Ｌ／ｈで供給しつつ、ｐＨ１１．３となるように水酸化ナトリウム水溶液を供給した。このとき、適宜、各槽内の溶液重量を測定し流量を調節した。
次に、４８時間後にオーバーフローしてきた試料を回収し、濾過および水洗を行い、１２０℃で一晩乾燥させた。
(Example 7)
Ni:Co:Al molar ratio is 82:15:3 and the metal ion concentration is 1.5 mol/L nickel sulfate, a mixed solution of cobalt sulfate and aluminum sulfate, ammonium ion concentration is 4 mol/L ammonia water, And a 20 wt% sodium hydroxide aqueous solution were prepared. Concentrated sulfuric acid was added to a mixed solution of nickel sulfate, cobalt sulfate and aluminum sulfate so that the pH became 3.0.
Next, 10 L of water was poured into a reaction tank having a capacity up to the overflow port of 10 L, and stirring was performed while controlling the temperature in the reaction tank to 50°C. While supplying the mixed sulfate aqueous solution of nickel and cobalt at 0.76 L/h and the aqueous ammonia at 0.3 L/h, an aqueous sodium hydroxide solution was supplied so that pH was 11.3. At this time, the weight of the solution in each tank was appropriately measured and the flow rate was adjusted.
Next, after 48 hours, the overflowed sample was collected, filtered, washed with water, and dried overnight at 120°C.
（実施例８）
実施例７のＮｉ：Ｃｏ：Ａｌのモル比を８５：１２：３としたこと、および、ｐＨを２．５とした以外は、実施例７と同じ条件とした。
(Example 8)
The conditions were the same as in Example 7 except that the Ni:Co:Al molar ratio of Example 7 was 85:12:3 and the pH was 2.5.
（実施例９）
実施例７のＮｉ：Ｃｏ：Ａｌのモル比を７５：２０：５としたこと、および、ｐＨを１．０とした以外は、実施例７と同じ条件とした。
(Example 9)
The conditions were the same as in Example 7 except that the molar ratio of Ni:Co:Al in Example 7 was 75:20:5 and the pH was 1.0.
実施例２〜９についても実施例１と同様に、組成式がＮｉ1-x-yＣｏxＭyＡｌz（ＯＨ）2+α
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表されるニッケルコバルトアルミニウム複合水酸化物粒子が得られた。
In the same manner as in Example 1 even for Examples 2-9, composition formula Ni 1-xy Co x M y Al z (OH) 2 + α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, and M is Mn or Zr). Cobalt-aluminum composite hydroxide particles were obtained.
（比較例１）
実施例１の硫酸アルミニウムに変えて、アルミン酸ナトリウムとした以外は実施例１と同じ条件とした。
(Comparative Example 1)
The conditions were the same as in Example 1 except that sodium aluminate was used instead of aluminum sulfate in Example 1.
（比較例２）
Ｎｉ：Ｃｏ：Ａｌのモル比が８２：１５：３であって金属イオン濃度が１．５ｍｏｌ／Ｌの硫酸ニッケル、硫酸コバルトおよび硫酸アルミニウムの混合溶液（ｐＨ４．５）、アンモニウムイオン濃度が４ｍｏｌ／Ｌのアンモニア水、および２０ｗｔ％の水酸化ナトリウム水溶液を調整した。
次に、オーバーフロー口までの容量が１０Ｌである反応槽に１０Ｌの水を張り、反応槽内の温度を５０℃に制御しつつ撹拌を行った。これに上記ニッケルおよびコバルトの混合硫酸塩水溶液を０．７６Ｌ／ｈ、アンモニア水を０．６Ｌ／ｈで供給しつつ、ｐＨ１０．３となるように水酸化ナトリウム水溶液を供給した。
次に、４８時間後にオーバーフローしてきた試料を回収し、濾過および水洗を行い、１２０℃で一晩乾燥させたところ、ニッケルコバルトアルミニウム複合水酸化物粒子が得られた。
(Comparative example 2)
Ni:Co:Al molar ratio is 82:15:3 and metal ion concentration is 1.5 mol/L nickel sulfate, cobalt sulfate and aluminum sulfate mixed solution (pH 4.5), ammonium ion concentration is 4 mol/L. L ammonia water and 20 wt% sodium hydroxide aqueous solution were prepared.
Next, 10 L of water was poured into a reaction tank having a capacity up to the overflow port of 10 L, and stirring was performed while controlling the temperature in the reaction tank to 50°C. While supplying the mixed sulfate aqueous solution of nickel and cobalt at 0.76 L/h and the aqueous ammonia at 0.6 L/h, an aqueous sodium hydroxide solution was supplied so that pH was 10.3.
Next, after 48 hours, the overflowed sample was collected, filtered, washed with water, and dried at 120° C. overnight to obtain nickel-cobalt-aluminum composite hydroxide particles.
＜水酸化物粒子の分析＞
実施例及び比較例によって得られたニッケルコバルトアルミニウム複合水酸化物粒子の金属元素の組成比（モル比）を、誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）で測定した。
<Analysis of hydroxide particles>
The composition ratio (molar ratio) of the metal elements in the nickel-cobalt-aluminum composite hydroxide particles obtained in the examples and comparative examples was measured by an inductively coupled plasma optical emission spectrometer (ICP-OES).
＜水酸化物粒子の平均粒径（Ｄ５０）＞
実施例及び比較例によって得られたニッケルコバルトアルミニウム複合水酸化物粒子の平均粒径（Ｄ５０）を、レーザー回折式粒子径分布測定によって測定した。
<Average particle size of hydroxide particles (D50)>
The average particle diameter (D50) of the nickel-cobalt-aluminum composite hydroxide particles obtained in Examples and Comparative Examples was measured by laser diffraction particle size distribution measurement.
実施例及び比較例の試験条件及び得られたニッケルコバルトアルミニウム複合水酸化物粒子の金属元素の組成及び粒径を表１に示す。 Table 1 shows the test conditions of Examples and Comparative Examples and the composition and particle size of the metal element of the obtained nickel-cobalt-aluminum composite hydroxide particles.
実施例１、６〜９、参考例２〜５はいずれも所望の粒径のニッケルコバルトアルミニウム複合水酸化物粒子を安定して製造することができた。具体的には、実施例１、６〜９、参考例２〜５はいずれも所望の粒径のニッケルコバルトアルミニウム複合水酸化物粒子を製造することができ、試験開始から３０日以上経過しても水溶液の濃度変化及び反応液の供給ポンプの詰まりが生じなかった。
比較例１は、試験開始から２４時間程度経過したあたりから水酸化アルミニウムの析出が始まり、試験開始から４８時間後でニッケルコバルトアルミニウム複合水酸化物粒子の粒径が２０μｍとなり、水溶液中のアルミニウムイオン濃度の低下が生じるとともに、徐々に粒径が減少していき、試験開始から１０日後の粒径が６μｍと小さくなり、試験開始から１０日目で反応液の供給ポンプに詰まりが生じた。
比較例２は、ｐＨ３．０を超える硫酸ニッケル及び硫酸コバルトの混合溶液に、硫酸アルミニウムを加えた後、当該混合溶液と水酸化ナトリウム水溶液とアンモニア水とをそれぞれ個別に反応槽に供給して反応させたため、反応槽内に水酸化アルミニウムの微粒子が生じた。反応槽内ではこの微粒子が核となり粒子が成長したため、粒子数が多くなり、あまり成長せず、４μｍという小さな粒径のニッケルコバルトアルミニウム複合水酸化物粒子が得られた。
In each of Examples 1 , 6 to 9 and Reference Examples 2 to 5 , nickel cobalt aluminum composite hydroxide particles having a desired particle size could be stably produced. Specifically, all of Examples 1 , 6 to 9 and Reference Examples 2 to 5 can produce nickel cobalt aluminum composite hydroxide particles having a desired particle size, and 30 days or more have passed from the start of the test. Also, the concentration change of the aqueous solution and the clogging of the reaction solution supply pump did not occur.
In Comparative Example 1, the precipitation of aluminum hydroxide started around 24 hours after the start of the test, and the particle size of the nickel-cobalt-aluminum composite hydroxide particles became 20 μm 48 hours after the start of the test. As the concentration decreased, the particle size gradually decreased, and the particle size after 10 days from the start of the test became as small as 6 μm, and the reaction solution supply pump was clogged 10 days after the start of the test.
In Comparative Example 2, after aluminum sulfate was added to a mixed solution of nickel sulfate and cobalt sulfate having a pH of more than 3.0, the mixed solution, a sodium hydroxide aqueous solution, and ammonia water were individually supplied to a reaction tank for reaction. As a result, fine particles of aluminum hydroxide were generated in the reaction tank. In the reaction tank, since the fine particles became nuclei and grew, the number of particles increased, and the particles did not grow so much, and nickel cobalt aluminum composite hydroxide particles having a small particle diameter of 4 μm were obtained.
１ 金属塩
２ 苛性ソーダ
３ アンモニア水または硫安
1 Metal salt 2 Caustic soda 3 Ammonia water or ammonium sulfate
Claims (4)
（式中、０．０５＜ｘ＜０．２０、０≦ｙ＜０．１、０＜ｚ＜０．０５、０≦α≦１、ＭはＭｎ又はＺｒである。）で表される水酸化物粒子の製造方法であって、
ニッケル塩及びコバルト塩の混合溶液に、硫酸アルミニウムまたは硝酸アルミニウムを加えて、ｐＨ３．０以下に調製した後、前記混合溶液とアルカリ金属水酸化物水溶液とアンモニウムイオンを含む水溶液とをそれぞれ個別に反応槽に供給して反応させる工程を含むニッケルコバルトアルミニウム複合水酸化物粒子の製造方法。 Composition formula Ni 1-xy Co x M y Al z (OH) 2 + α
(Wherein 0.05<x<0.20, 0≦y<0.1, 0<z<0.05, 0≦α≦1, M is Mn or Zr). A method for producing oxide particles, comprising:
Aluminum sulfate or aluminum nitrate is added to a mixed solution of a nickel salt and a cobalt salt to adjust the pH to 3.0 or less, and then the mixed solution, an alkali metal hydroxide aqueous solution and an aqueous solution containing ammonium ion are individually reacted. A method for producing nickel-cobalt-aluminum composite hydroxide particles, comprising the step of supplying the nickel-cobalt-aluminum composite hydroxide to a reaction vessel.
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