JP2021064581A - Positive electrode active material for lithium ion secondary battery and manufacturing method thereof - Google Patents
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 72
- 239000002905 metal composite material Substances 0.000 claims abstract description 39
- 210000004556 brain Anatomy 0.000 claims abstract description 28
- 239000010419 fine particle Substances 0.000 claims abstract description 17
- 238000000790 scattering method Methods 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- -1 ammonium ions Chemical class 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 42
- 238000001914 filtration Methods 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000000243 solution Substances 0.000 description 38
- 230000008569 process Effects 0.000 description 34
- 239000000047 product Substances 0.000 description 34
- 230000001590 oxidative effect Effects 0.000 description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 24
- 238000001035 drying Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 15
- 229920002472 Starch Polymers 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 235000019698 starch Nutrition 0.000 description 13
- 239000008107 starch Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000000523 sample Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000007561 laser diffraction method Methods 0.000 description 9
- 150000002642 lithium compounds Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000007788 liquid Substances 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009295 crossflow filtration Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910015014 LiNiCoAlO Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003149 assay kit Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012284 sample analysis method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
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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、リチウムイオン二次電池用正極活物質に関する。 The present invention relates to a positive electrode active material for a lithium ion secondary battery.
現在、リチウムイオン二次電池は、軽量でエネルギー密度が高いことから、スマートフォンやタブレット、ミニノートパソコン、その他、ＩＴ機器などの小型電池に幅広く使用されており、ＩＴ機器の発展・普及に伴い、現在も、その需要が世界的な規模で急増している。これらの小型電池には、ＬｉＣｏＯ２をはじめ、ＬｉＮｉＭｎＣｏＯ２、ＬｉＮｉＣｏＡｌＯ２などの層状岩塩化合物からなる正極活物質が用いられている。更に、これらの小型電池に加えて、産業用の大型電池として、ハイブリッド自動車（ＨＥＶ）用や、電力貯蔵用など、多方面に需要の拡大が期待されている。
この様な需要環境の中で、車載用・産業用の大型電池が本格的に普及するための課題として、正極材料には、高い安全性、高寿命、高出力、低価格が要求されている。
リチウムイオン二次電池用の正極活物質の製造方法は、まず、ニッケル、マンガン、コバルトなどの遷移金属元素をベースとして含有し、開発ニーズに応じてアルミニウム、亜鉛、錫などの典型金属元素を加えた原料溶液を、中和晶析法によりアルカリと中和反応させることで、前駆体となる金属複合水酸化物を主成分（固形分）とするスラリーが得られる。続いて、このスラリーを、フィルタープレスなどの濾過機を用いて濾過し、固液分離することで、金属複合水酸化物の含水澱物が得られる。そして、この含水澱物を乾燥することで、前駆体となる金属複合水酸化物が得られ、金属複合水酸化物をリチウム化合物と混合し、リチウム混合物として焼成・アニール処理することで、正極活物質となるリチウム金属複合酸化物が得られる。
前駆体となる金属複合水酸化物粒子の形状などの特徴は、正極活物質となるリチウム金属複合酸化物粒子に、ほぼ引き継がれ、粒子形状のほか、粒度分布や一次粒子及び二次粒子の粒径などに大きく影響する。これらのリチウム金属複合酸化物粒子の特徴は、カーボン粉などの導電材やＰＶＤＦなどの結着材と共に正極材料に組み入れた後、リチウムイオン二次電池の性能・特性に直結する重要な要素となることから、前駆体となる金属複合水酸化物粒子の粒子形状、粒度分布、一次粒子及び二次粒子の粒径などが、安定して製造出来なければならない。
しかし、上記の製造方法においては、中和晶析法で得られる、スラリー中の金属複合水酸化物からなる固形分に、平均粒径が０．０１〜１．０μｍレベルの微細粒子が、乾燥状態の水酸化物に対して、最大で０．５質量％程度含まれる場合がある。このため、粒子の平均粒径が不安定となるほか、微細粒子により濾過操作で濾布フィルターが目詰りを起こし、濾過性が悪化して濾過工程が律速になることがあった。この微細粒子が発生するメカニズムについては、未だ、明確に解明されておらず、晶析反応における各条件の変動のほか、反応溶液の撹拌方法や撹拌速度の変動など、幾つかの因子が複合的に重なることにより、表面化するものと考えられている。
この様な現象に対し、特許文献１では、クロスフロー濾過を採用することで、目詰りへの対策としている。クロスフロー濾過とは、筒状の膜フィルターを使用し、固形分を含む原液スラリーを濾過対象液として膜フィルターの内部に供給し、膜フィルターを透過した濾液を膜フィルターの外面から回収すると共に、原液スラリー中の固形分の濃縮を行う濾過方法である。
Currently, lithium-ion secondary batteries are lightweight and have high energy density, so they are widely used in small batteries such as smartphones, tablets, mini-notebook computers, and other IT devices. With the development and spread of IT devices, Even now, the demand is rapidly increasing on a global scale. For these small batteries, a positive electrode active material composed of layered rock salt compounds such as LiCoO 2 , LiNiMnCoO 2 , and LiNiCoAlO 2 is used. Further, in addition to these small batteries, demand for large industrial batteries is expected to increase in various fields such as for hybrid electric vehicles (HEV) and for power storage.
In such a demand environment, high safety, long life, high output, and low price are required for positive electrode materials as issues for the full-scale spread of large batteries for automobiles and industries. ..
The method for producing a positive electrode active material for a lithium ion secondary battery first contains transition metal elements such as nickel, manganese, and cobalt as a base, and adds typical metal elements such as aluminum, zinc, and tin according to development needs. By neutralizing the raw material solution with an alkali by a neutralization crystallization method, a slurry containing a metal composite hydroxide as a precursor as a main component (solid content) can be obtained. Subsequently, this slurry is filtered using a filter such as a filter press and solid-liquid separated to obtain a hydrous starch of a metal composite hydroxide. Then, by drying this hydrous starch, a metal composite hydroxide as a precursor is obtained, and the metal composite hydroxide is mixed with a lithium compound and fired and annealed as a lithium mixture to activate the positive electrode. A lithium metal composite oxide as a substance can be obtained.
Features such as the shape of the metal composite hydroxide particles that serve as precursors are almost inherited by the lithium metal composite oxide particles that serve as the positive electrode active material. It greatly affects the diameter. The characteristics of these lithium metal composite oxide particles become an important factor that is directly linked to the performance and characteristics of the lithium ion secondary battery after being incorporated into the positive electrode material together with the conductive material such as carbon powder and the binder material such as PVDF. Therefore, the particle shape, particle size distribution, particle size of the primary particles and the secondary particles of the metal composite hydroxide particles as the precursor must be stably produced.
However, in the above production method, fine particles having an average particle size of 0.01 to 1.0 μm are dried on the solid content of the metal composite hydroxide in the slurry obtained by the neutralization crystallization method. It may be contained in a maximum of about 0.5% by mass with respect to the hydroxide in the state. For this reason, the average particle size of the particles becomes unstable, and the filter cloth filter may be clogged by the filtration operation due to the fine particles, resulting in deterioration of the filterability and a rate-determining process in the filtration process. The mechanism by which these fine particles are generated has not yet been clarified, and several factors such as fluctuations in each condition in the crystallization reaction, fluctuations in the stirring method of the reaction solution, and fluctuations in the stirring speed are complex. It is thought that it will surface by overlapping with.
In response to such a phenomenon, Patent Document 1 uses cross-flow filtration as a countermeasure against clogging. In cross-flow filtration, a tubular membrane filter is used, and a stock solution slurry containing solids is supplied to the inside of the membrane filter as a filter target liquid, and the filtrate that has passed through the membrane filter is collected from the outer surface of the membrane filter, and at the same time. This is a filtration method for concentrating the solid content in the undiluted solution slurry.
けれども、特許文献１の様に、濾過工程の改善のみでは、微細粒子の発生を抑制する抜本的な解決には繋がらない。そこで、本発明は、微細粒子の発生を極力抑制し、粒子の平均粒径が不安定になることや、濾過工程が律速になる問題を解消し、特性が安定したリチウム金属複合酸化物粒子を得ることを目的とする。 However, as in Patent Document 1, improvement of the filtration process alone does not lead to a drastic solution of suppressing the generation of fine particles. Therefore, the present invention solves the problems that the generation of fine particles is suppressed as much as possible, the average particle size of the particles becomes unstable, and the filtration process becomes rate-determining, and the lithium metal composite oxide particles having stable characteristics can be obtained. The purpose is to get.
本発明者は、上記課題を解決するため、リチウム金属複合酸化物及びその製造に関して鋭意研究を行った。その結果、晶析反応時、金属複合水酸化物粒子が生成する過程において、反応槽内の反応溶液を撹拌する方式を、従来の羽根式から遠心式に変更することで、微細粒子の発生を抑制し、濾過操作がスムーズに行えると共に、ひいては、最終的に、粒子の平均粒径や比表面積など、特性が安定したリチウム金属複合酸化物粒子が得られることを見出して、本発明を完成させるに至った。
なお、ここで、レーザー回折・散乱法による平均粒径ＭＶと、フィッシャー空気透過法によるＦｓｓｓ平均粒径の比であるＭＶ／Ｆｓｓｓのほか、ガス吸着法によるＢＥＴ比表面積と、ブレーン空気透過法によるブレーン比表面積の比であるＢＥＴ／ブレーンは、特性が安定したリチウム金属複合酸化物粒子が得られたことを確認するための重要な指標となる。
即ち、上記の知見に基づいてなされた、本発明の態様は、以下の通りである。
本発明に係る第１の態様は、
レーザー回折・散乱法による平均粒径ＭＶと、フィッシャー空気透過法によるＦｓｓｓ平均粒径の比であるＭＶ／Ｆｓｓｓが、０．６０〜１．８０であり、ガス吸着法によるＢＥＴ比表面積と、ブレーン空気透過法によるブレーン比表面積の比であるＢＥＴ／ブレーンが、０．６０〜１．６０であることを特徴とするリチウムイオン二次電池用正極活物質である。
本発明に係る第２の態様は、第１の態様に記載の発明において、
１μｍ以下の微細粒子の含有量が、０．１５質量％未満であり、タップ密度が、１．５０〜３．００ｇ／ｃｍ３であることを特徴とするリチウムイオン二次電池用正極活物質である。
本発明に係る第３の態様は、第１又は第２の態様に記載の発明において、
一般式：ＬｉｓＮｉ１−ｘ−ｙＣｏｘＭｙＯ２＋α
（式中、ｓ、ｘ、ｙ及びαは、それぞれ０．９５≦ｓ≦１．３０、０．０５≦ｘ≦０．３５、０≦ｙ≦０．４５及び０≦α≦０．２を満たす数、Ｍは、Ｍｎ、Ａｌ、Ｗ、Ｍｏ、Ｎｂからなる群より選ばれた、少なくとも１種の金属元素を示す）で表されることを特徴とするリチウムイオン二次電池用正極活物質である。
本発明に係る第４の態様は、
遷移金属元素を含む溶液、典型金属元素を含む溶液、遷移金属及び典型金属元素を含む溶液のいずれかの溶液と、アルカリと、アンモニウムイオンを混合して、金属複合水酸化物を含むスラリーを得る晶析工程を有し、前記混合には、遠心式撹拌機を用いることを特徴とするリチウムイオン二次電池用正極活物質の製造方法である。
In order to solve the above problems, the present inventor has conducted diligent research on lithium metal composite oxides and their production. As a result, in the process of forming metal composite hydroxide particles during the crystallization reaction, the method of stirring the reaction solution in the reaction vessel is changed from the conventional vane type to the centrifugal type to generate fine particles. The present invention is completed by finding that lithium metal composite oxide particles having stable characteristics such as the average particle size and specific surface area of the particles can be finally obtained while suppressing and smoothly performing the filtration operation. It came to.
Here, in addition to MV / Fsss, which is the ratio of the average particle size MV by the laser diffraction / scattering method and the Fss average particle size by the Fisher air permeation method, the BET specific surface area by the gas adsorption method, and the brain air permeation method. BET / brain, which is the ratio of the specific surface area of the brain, is an important index for confirming that the lithium metal composite oxide particles having stable characteristics have been obtained.
That is, the aspects of the present invention made based on the above findings are as follows.
The first aspect according to the present invention is
The MV / Fsss, which is the ratio of the average particle size MV by the laser diffraction / scattering method and the Fsss average particle size by the Fisher air permeation method, is 0.60 to 1.80, and the BET specific surface area by the gas adsorption method and the brain. A positive electrode active material for a lithium ion secondary battery, characterized in that the BET / brain, which is the ratio of the specific surface area of the brain by the air permeation method, is 0.60 to 1.60.
A second aspect of the present invention is the invention described in the first aspect.
A positive electrode active material for a lithium ion secondary battery, characterized in that the content of fine particles of 1 μm or less is less than 0.15% by mass and the tap density is 1.50 to 3.00 g / cm 3. is there.
A third aspect of the present invention is the invention described in the first or second aspect.
Formula: Li s Ni 1-x- y Co x M y O 2 + α
(In the formula, s, x, y and α have 0.95 ≦ s ≦ 1.30, 0.05 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.45 and 0 ≦ α ≦ 0.2, respectively. The number to be satisfied, M, represents at least one metal element selected from the group consisting of Mn, Al, W, Mo, and Nb). Is.
The fourth aspect according to the present invention is
A solution containing a transition metal element, a solution containing a typical metal element, or a solution containing a transition metal or a typical metal element is mixed with an alkali and ammonium ions to obtain a slurry containing a metal composite hydroxide. It is a method for producing a positive electrode active material for a lithium ion secondary battery, which comprises a crystallization step and uses a centrifugal stirrer for the mixing.
本発明を適用すれば、リチウム金属複合酸化物粒子の平均粒径及び比表面積について、２つの評価方法の分析値の比を最適化でき、特性を安定させることが出来る。また、微細粒子の発生を極力抑制でき、粒子の平均粒径が不安定になることや、濾過工程が律速になる問題を解消し、特性が安定したリチウム金属複合酸化物を効率良く製造することが可能となる。 By applying the present invention, it is possible to optimize the ratio of the analytical values of the two evaluation methods for the average particle size and the specific surface area of the lithium metal composite oxide particles, and to stabilize the characteristics. In addition, it is possible to suppress the generation of fine particles as much as possible, solve the problems that the average particle size of the particles becomes unstable and the filtration process becomes rate-determining, and efficiently produce a lithium metal composite oxide with stable characteristics. Is possible.
はじめに、本発明の実施形態について、その概要を説明する。 First, the outline of the embodiment of the present invention will be described.
本発明における、リチウムイオン二次電池用正極活物質の製造方法では、まず、遷移金属元素を含む溶液、典型金属元素を含む溶液、遷移金属元素及び典型金属元素を含む溶液のいずれかの溶液に、アルカリを連続的に供給しながら、目的とする粒子構造（中実、中空、多孔）によって、晶析反応の雰囲気を非酸化性、又は、酸化性に適宜制御すると共に、所定の温度、ｐＨ、アンモニウムイオン（ＮＨ４ ＋）濃度などを維持して、金属複合水酸化物（以降、単に「水酸化物」とも記載する）粒子を生成させる。 In the method for producing a positive electrode active material for a lithium ion secondary battery in the present invention, first, a solution containing a transition metal element, a solution containing a typical metal element, or a solution containing a transition metal element and a typical metal element is prepared. , While continuously supplying alkali, the atmosphere of the crystallization reaction is appropriately controlled to be non-oxidizing or oxidative by the target particle structure (solid, hollow, porous), and a predetermined temperature and pH. , to maintain such ammonium ions (NH 4 +) concentration, metal complex hydroxide (hereinafter, simply referred to as "hydroxide") to produce particles.
そして、金属複合水酸化物粒子の生成において、反応槽内の反応溶液を遠心式撹拌機で撹拌後、濾過性を保ちつつ濾過を行い、濾過後の含水澱物を、所定の温度で乾燥することにより、金属複合水酸化物を含む乾燥物（前駆体）を得るものである。 Then, in the formation of the metal composite hydroxide particles, the reaction solution in the reaction vessel is stirred with a centrifugal stirrer, filtered while maintaining the filterability, and the filtered hydrous starch is dried at a predetermined temperature. As a result, a dried product (precursor) containing a metal composite hydroxide is obtained.
次に、上記の乾燥物を、所定の温度で酸化焙焼することにより、粒子強度が良好な酸化焙焼物（中間物）を得る。 Next, the dried product is oxidatively roasted at a predetermined temperature to obtain an oxidative roasted product (intermediate) having good particle strength.
更に、上記の酸化焙焼物とリチウム化合物とを混合し、リチウム混合物として、所定の温度で焼成することにより、粒子強度が維持された焼成物となり、かつ、この焼成物の表面に存在している余剰リチウム（即ち、水酸化リチウム及び炭酸リチウム）を水洗し、粒子の平均粒径など、特性が安定したリチウム金属複合酸化物（正極活物質）を得る。 Further, the above-mentioned oxidized roasted product and the lithium compound are mixed and fired as a lithium mixture at a predetermined temperature to obtain a fired product in which the particle strength is maintained, and the calcined product exists on the surface of the fired product. Excess lithium (that is, lithium hydroxide and lithium carbonate) is washed with water to obtain a lithium metal composite oxide (positive electrode active material) having stable characteristics such as the average particle size of the particles.
次に、本発明における一実施形態を、下記の順序の通り、詳細に説明する。
１．リチウムイオン二次電池用正極活物質前駆体の製造方法
２．リチウムイオン二次電池用正極活物質中間物の製造方法
３．リチウムイオン二次電池用正極活物質の製造方法
４．１〜３に関する評価
本発明に係る、リチウムイオン二次電池用正極活物質及びその製造方法は、決して、以下の説明に限定されるものではなく、本発明の趣旨から逸脱しない限り、当業者の知識に基づいて、実施形態を多様に改変することが出来る。
１．リチウムイオン二次電池用正極活物質前駆体の製造方法
＜金属複合水酸化物の製造工程＞
［晶析工程］
まず、原料溶液として、ニッケル、マンガン、コバルトなどの遷移金属元素や、アルミニウム、亜鉛、錫などの典型金属元素からなる、金属化合物の水溶液（これら水溶液の作製には、硫酸塩及び水和物を用いるのが好ましい）を混合して作製した金属複合溶液と、ｐＨ調整用のアルカリ（水酸化ナトリウム溶液など）と、アンモニウムイオン（ＮＨ４ ＋）濃度調整用のアンモニア水を準備する。
次に、加熱によって４０〜６０℃となる様に制御された、反応槽内の水（イオン交換水などの様な、不純物が制御された純水が好ましい）を遠心式撹拌機で撹拌しながら、引き続き晶析処理を行う。遠心式撹拌機の回転で、その吐出口に遠心力が発生し、溶液が吐出され、かつ、その縦流路内に負圧が発生し、竜巻状の吸引流が起こる。吐出された溶液は、反応槽壁面に当たって上下に循環し、反応槽内全体に行き渡って均一に撹拌される。
その際に粒子構造を「中実」としたい場合は、反応槽上部から窒素ガスなどの不活性ガスを導入し、反応槽内を非酸化性雰囲気（酸素濃度１．０容積％以下）に、「中空」若しくは「多孔」としたい場合は、反応槽内を酸化性雰囲気（大気雰囲気が好ましい）として、反応槽内の水のｐＨが１０．５〜１３．５となる様に、水酸化ナトリウム溶液の給液量を制御しながら、金属複合溶液とアンモニア水を一定速度で給液し、反応溶液を作製して、晶析処理を０．５時間以下で行う。
上記の晶析処理の後、粒子構造を「中実」、「中空」、「多孔」のいずれかにするには、次の様な条件を選択、設定して、引き続き処理を行う。
Next, one embodiment of the present invention will be described in detail in the following order.
1. 1. Method for manufacturing positive electrode active material precursor for lithium ion secondary battery 2. 2. Manufacturing method of positive electrode active material intermediate for lithium ion secondary batteries. Evaluation of Method for Producing Positive Electrode Active Material for Lithium Ion Secondary Battery 4.1 to 3 The positive electrode active material for lithium ion secondary battery and its manufacturing method according to the present invention are by no means limited to the following description. Without deviating from the gist of the present invention, the embodiments can be variously modified based on the knowledge of those skilled in the art.
1. 1. Manufacturing method of positive electrode active material precursor for lithium ion secondary battery <Manufacturing process of metal composite hydroxide>
[Crystalization process]
First, as a raw material solution, an aqueous solution of a metal compound composed of transition metal elements such as nickel, manganese and cobalt and typical metal elements such as aluminum, zinc and tin (sulfates and hydrates are used to prepare these aqueous solutions. a metal complex solution prepared by mixing preferably) used to prepare the alkali for pH adjustment (such as sodium hydroxide solution), the ammonium ions (NH 4 +) ammonia water for adjusting the concentration.
Next, while stirring the water in the reaction vessel (preferably pure water with controlled impurities such as ion-exchanged water) controlled to be 40 to 60 ° C. by heating with a centrifugal stirrer. , Continue the crystallization treatment. When the centrifugal stirrer rotates, a centrifugal force is generated at the discharge port, the solution is discharged, and a negative pressure is generated in the vertical flow path, and a tornado-shaped suction flow is generated. The discharged solution hits the wall surface of the reaction vessel and circulates up and down, and is uniformly agitated throughout the inside of the reaction vessel.
At that time, if the particle structure is to be "solid", an inert gas such as nitrogen gas is introduced from the upper part of the reaction tank to create a non-oxidizing atmosphere (oxygen concentration 1.0% by volume or less) in the reaction tank. If you want to make it "hollow" or "porous", create an oxidizing atmosphere (preferably an air atmosphere) in the reaction vessel, and sodium hydroxide so that the pH of the water in the reaction vessel is 10.5-13.5. While controlling the amount of the solution to be supplied, the metal composite solution and aqueous ammonia are supplied at a constant rate to prepare a reaction solution, and the crystallization treatment is performed in 0.5 hours or less.
After the above crystallization treatment, in order to make the particle structure "solid", "hollow", or "porous", the following conditions are selected and set, and the treatment is continued.
粒子構造を「中実」としたい場合は、反応槽内を非酸化性雰囲気としたままで、晶析処理を４時間継続する。 If the particle structure is to be "solid", the crystallization treatment is continued for 4 hours while keeping the inside of the reaction vessel in a non-oxidizing atmosphere.
「中空」としたい場合は、各溶液の給液を止め、反応槽内を非酸化性雰囲気から酸化性雰囲気に切り替えた後、給液を再開して、晶析処理を４時間継続する。 If it is desired to be "hollow", the supply of each solution is stopped, the inside of the reaction vessel is switched from a non-oxidizing atmosphere to an oxidizing atmosphere, the supply is restarted, and the crystallization treatment is continued for 4 hours.
「多孔」としたい場合は、各溶液の給液を止め、反応槽内を非酸化性雰囲気から酸化性雰囲気に切り替えた後、給液を再開し、以降、同様の切り替え操作を複数回行いながら、晶析処理を４時間継続する。 If you want to make it "porous", stop the supply of each solution, switch the inside of the reaction tank from a non-oxidizing atmosphere to an oxidizing atmosphere, restart the supply, and then perform the same switching operation multiple times. , The crystallization treatment is continued for 4 hours.
この様に、反応槽内の雰囲気を、不活性雰囲気又は酸素濃度を１．０容積％以下に制御した非酸化性雰囲気、或いは、酸化性雰囲気（大気雰囲気）とすることで、金属複合水酸化物の粒子構造の制御が可能となっている。
ここで、反応槽内の温度が４０℃よりも低いと、金属複合水酸化物の粒径が大きくなり過ぎ、また、６０℃より高い場合は、逆に、金属複合水酸化物の粒径が小さくなり過ぎ、その影響が、後工程で製造されるリチウム金属複合酸化物にも現われるため、好ましくない。
なお、最初の反応槽内のｐＨが１０．５よりも小さい場合は、正極活物質に残存する硫酸塩濃度が高くなり、電池に組み込んだ際の出力特性が悪化するため、好ましくない。その一方、ｐＨが１３．５よりも大きい場合には、粒径が小さくなり過ぎるため、好ましくない。更には、アンモニウムイオン（ＮＨ４ ＋）濃度は、５〜３０ｇ／Ｌが好ましく、より好ましくは１０〜２０ｇ／Ｌに制御することで、晶析処理を安定させることが可能である。
In this way, the atmosphere in the reaction vessel is an inert atmosphere or a non-oxidizing atmosphere in which the oxygen concentration is controlled to 1.0% by volume or less, or an oxidizing atmosphere (atmospheric atmosphere), whereby metal composite hydroxylation is performed. It is possible to control the particle structure of an object.
Here, if the temperature in the reaction vessel is lower than 40 ° C., the particle size of the metal composite hydroxide becomes too large, and if it is higher than 60 ° C., on the contrary, the particle size of the metal composite hydroxide becomes large. It becomes too small, and its influence also appears in the lithium metal composite oxide produced in the subsequent process, which is not preferable.
If the pH in the initial reaction vessel is smaller than 10.5, the concentration of sulfate remaining in the positive electrode active material becomes high, and the output characteristics when incorporated into the battery deteriorate, which is not preferable. On the other hand, if the pH is higher than 13.5, the particle size becomes too small, which is not preferable. Furthermore, ammonium ion (NH 4 +) concentration is preferably 5 to 30 g / L is more preferably by controlling the 10 to 20 g / L, it is possible to stabilize the crystallization process.
その他、得られる金属複合水酸化物の空隙率が、それぞれの粒子構造に適した範囲でないと、好ましい粒子強度が維持出来ず、後の製造工程で解砕され易くなったり、電解液との接触面積が不十分となったりして、目的とする正極活物質を得ることは出来ない。例えば、粒子構造を「中実」としたい場合は、空隙率が２０％未満であることが好ましく、更には、５％未満であることがより好ましい。
［濾過工程］
晶析反応後の金属複合水酸化物を含むスラリーを、濾過装置の濾布フィルターに通じた後、得られた含水澱物を、水酸化ナトリウム溶液などのアルカリにより、アルカリ洗浄することで、硫酸イオン（ＳＯ４ ２−）や塩素イオン（Ｃｌ−）などの陰イオンを除去し、更に、イオン交換水などの様な、不純物が制御された純水で再度洗浄し、ナトリウムイオン（Ｎａ＋）などの陽イオンを除去する。
In addition, if the porosity of the obtained metal composite hydroxide is not in a range suitable for each particle structure, the preferable particle strength cannot be maintained, and it is easy to be crushed in a later manufacturing process, or contact with an electrolytic solution. The target positive electrode active material cannot be obtained due to insufficient area. For example, when the particle structure is desired to be "solid", the porosity is preferably less than 20%, more preferably less than 5%.
[Filtration process]
The slurry containing the metal composite hydroxide after the crystallization reaction is passed through a filter cloth filter of a filtering device, and then the obtained hydrous starch is washed with an alkali such as a sodium hydroxide solution to carry out sulfuric acid. ion (SO 4 2-) and chlorine ions (Cl -) anion such as removal, addition, such as such as ion exchange water, and washed again with pure water in which impurities are controlled, sodium ions (Na +) Removes cations such as.
なお、使用する濾過装置については、キャンドルフィルター、フィルタープレス、リーフフィルター、ドラムフィルターなどが挙げられ、特に限定されないが、フィルタープレスを用いての濾過がより好ましい。
［乾燥工程]
この乾燥工程は、濾過工程により得た含水澱物を乾燥し、乾燥物（前駆体）を得る工程である。この乾燥工程で、澱物に付着している水分を十分に除去することで、後工程の酸化焙焼工程を、より効率的に行うことが出来る。
その乾燥の温度は、１００〜２００℃が好ましく、１２０〜１８０℃がより好ましい。１００℃未満になると、温度が低く水分が蒸発され難くなるため、好ましくない。その一方で、２００℃を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。
The filtration device to be used includes a candle filter, a filter press, a leaf filter, a drum filter and the like, and is not particularly limited, but filtration using a filter press is more preferable.
[Drying process]
This drying step is a step of drying the hydrous starch obtained by the filtration step to obtain a dried product (precursor). By sufficiently removing the water adhering to the starch in this drying step, the post-step oxidative roasting step can be performed more efficiently.
The drying temperature is preferably 100 to 200 ° C, more preferably 120 to 180 ° C. If it is less than 100 ° C., the temperature is low and it becomes difficult for water to evaporate, which is not preferable. On the other hand, there is no particular problem even if the temperature exceeds 200 ° C., but it is not so preferable in consideration of manufacturing cost and efficiency.
また、乾燥の時間は、特に限定されるものではなく、上記の水分の除去が可能であればよいが、１〜５時間、乾燥を行うことが好ましい。１時間未満になると、時間が短すぎて水分が除去され難くなるため、好ましくない。その一方で、５時間を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。 The drying time is not particularly limited as long as the above-mentioned moisture can be removed, but it is preferable to carry out the drying for 1 to 5 hours. If it is less than 1 hour, the time is too short and it becomes difficult to remove water, which is not preferable. On the other hand, there is no particular problem even if it exceeds 5 hours, but it is not so preferable in consideration of manufacturing cost and efficiency.
更に、乾燥に使用する乾燥機についても、特に限定されるものではなく、静置式や、流動式、気流式のいずれの乾燥機も用いることができ、加熱方式については、乾燥雰囲気下の炭素ガスが増加しない、電気加熱方式が好ましい。
２．リチウムイオン二次電池用正極活物質中間物の製造方法
＜酸化焙焼物の製造工程＞
［酸化焙焼工程］
この酸化焙焼工程では、乾燥工程によって得た乾燥物を、大気雰囲気下により酸化焙焼し、酸化焙焼物（中間物）を得る。
Further, the dryer used for drying is not particularly limited, and any of a stationary type, a fluid type, and an air flow type dryer can be used, and the heating method is carbon gas in a dry atmosphere. The electric heating method is preferable because it does not increase.
2. Manufacturing method of positive electrode active material intermediate for lithium ion secondary battery <Manufacturing process of oxidized roasted product>
[Oxidation roasting process]
In this oxidative roasting step, the dried product obtained in the drying step is oxidatively roasted in an air atmosphere to obtain an oxidative roasted product (intermediate).
その酸化焙焼の温度は、８００〜１０００℃が好ましく、８００〜９００℃がより好ましい。８００℃未満になると、粒子強度が不十分となる恐れがあるため、好ましくない。一方、１０００℃を超えると、酸化焙焼物の粒子間で焼結が生じ、粒子が粗大化する場合があるため、好ましくない。 The oxidative roasting temperature is preferably 800 to 1000 ° C, more preferably 800 to 900 ° C. If the temperature is lower than 800 ° C., the particle strength may be insufficient, which is not preferable. On the other hand, if the temperature exceeds 1000 ° C., sintering occurs between the particles of the oxidized roasted product, and the particles may become coarse, which is not preferable.
また、酸化焙焼の時間は、１〜５時間が好ましい。１時間未満になると、粒子強度が不十分となる恐れがあるため、好ましくない。一方、５時間を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。
この酸化焙焼工程では、水分を完全に除去しつつ、粒子強度を更に高めるため、酸化焙焼に際して仮焼工程を加え、まず、４００〜５５０℃で１〜３時間、仮焼することが好ましい。また、仮焼の温度は、４５０〜５００℃とすることがより好ましい。４００℃未満、及び５５０℃を超えると、上記の効果を得難くなるため、好ましくない。
The time for oxidative roasting is preferably 1 to 5 hours. If it is less than 1 hour, the particle strength may be insufficient, which is not preferable. On the other hand, even if it exceeds 5 hours, there is no particular problem, but it is not so preferable in consideration of manufacturing cost and efficiency.
In this oxidative roasting step, in order to further increase the particle strength while completely removing water, it is preferable to add a calcination step at the time of oxidative roasting and first calcinate at 400 to 550 ° C. for 1 to 3 hours. .. Further, the temperature of the calcining is more preferably 450 to 500 ° C. If the temperature is lower than 400 ° C. and higher than 550 ° C., it becomes difficult to obtain the above effects, which is not preferable.
なお、仮焼の時間は、１〜３時間が好ましい。１時間未満になると、上記の効果を得難くなるため、好ましくない。一方で、３時間を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。 The calcining time is preferably 1 to 3 hours. If it is less than 1 hour, it becomes difficult to obtain the above effect, which is not preferable. On the other hand, there is no particular problem even if it exceeds 3 hours, but it is not so preferable in consideration of manufacturing cost and efficiency.
更に、酸化焙焼工程で使用する高温加熱炉は、特に限定されるものではなく、大気雰囲気下で加熱可能であればよいが、ガスが発生する心配の無い電気炉が好ましく、バッチ式か、若しくは連続式の炉が用いられる。
３．リチウムイオン二次電池用正極活物質の製造方法
＜リチウム金属複合酸化物の製造工程＞
［リチウム化合物］
リチウムの原料となるリチウム化合物は、最大粒径が１０μｍ以下であるのが好ましく、平均粒径が５μｍ以下であるのが好ましい。
Further, the high-temperature heating furnace used in the oxidative roasting step is not particularly limited as long as it can be heated in an atmospheric atmosphere, but an electric furnace that does not generate gas is preferable, and a batch type or a batch type is used. Alternatively, a continuous furnace is used.
3. 3. Manufacturing method of positive electrode active material for lithium ion secondary battery <Manufacturing process of lithium metal composite oxide>
[Lithium compound]
The lithium compound used as a raw material for lithium preferably has a maximum particle size of 10 μm or less, and preferably an average particle size of 5 μm or less.
また、リチウム化合物の種類は、特に制限されないが、炭酸リチウム（Ｌｉ２ＣＯ３：融点７２３℃）や、水酸化リチウム（ＬｉＯＨ：融点４６２℃）のほか、硝酸リチウム（ＬｉＮＯ３：融点２６１℃）や、塩化リチウム（ＬｉＣｌ：融点６１３℃）、硫酸リチウム（Ｌｉ２ＳＯ４：融点８５９℃）などが用いることが出来る。特に、取り扱いの容易さや品質安定性を考慮すると、水酸化リチウム又は炭酸リチウムを用いることが好ましい。
［混合工程］
この混合工程は、酸化焙焼工程後の酸化焙焼物とリチウム化合物とを混合し、リチウム混合物を得る工程である。
The type of lithium compound is not particularly limited, but is limited to lithium carbonate (Li 2 CO 3 : melting point 723 ° C.), lithium hydroxide (LiOH: melting point 462 ° C.), and lithium nitrate (LiNO 3 : melting point 261 ° C.). , Lithium chloride (LiCl: melting point 613 ° C.), lithium sulfate (Li 2 SO 4 : melting point 859 ° C.) and the like can be used. In particular, considering ease of handling and quality stability, it is preferable to use lithium hydroxide or lithium carbonate.
[Mixing process]
This mixing step is a step of mixing the oxidative roasted product after the oxidative roasting step with the lithium compound to obtain a lithium mixture.
この混合工程では、酸化焙焼物とリチウム化合物は、後工程で得られる、リチウム金属複合酸化物中の遷移金属元素及び典型金属元素の原子数の和とリチウムの原子数との比が、０．９５〜１．３０の範囲内で所定比率となる様に混合する。この比が０．９５より小さい場合には、リチウムサイトである３ａサイトにリチウム原子が取り込まれないため、製造されたリチウム金属複合酸化物を、正極活物質として電池に組み込んだ際に、目標とする電池特性が得られない。
ここで、サイトとは、結晶学的に等価な格子位置のことを言うもので、その格子位置に、ある原子が存在する場合は、「サイトが占有される」と言い、そのサイトは「占有サイト」と呼ばれる。例えば、ＬｉＣｏＯ２には、３つの占有サイトが存在し、それぞれリチウムサイト、コバルトサイト、酸素サイトと呼ばれ、或いは、３ａサイト、３ｂサイト、６ｃサイトなどとも呼ばれる。
In this mixing step, the oxidized roasted product and the lithium compound have a ratio of the sum of the atomic numbers of the transition metal element and the typical metal element in the lithium metal composite oxide obtained in the subsequent step to the number of lithium atoms. Mix so as to have a predetermined ratio within the range of 95 to 1.30. If this ratio is less than 0.95, lithium atoms are not incorporated into the 3a site, which is a lithium site. Therefore, when the produced lithium metal composite oxide is incorporated into a battery as a positive electrode active material, the target is set. Battery characteristics are not obtained.
Here, the site refers to a crystallographically equivalent lattice position, and when a certain atom exists at the lattice position, it is said that "the site is occupied" and the site is "occupied". It is called "site". For example, LiCoO 2 has three occupied sites, which are called lithium sites, cobalt sites, oxygen sites, or 3a sites, 3b sites, 6c sites, and the like, respectively.
また、上記の比が１．３０より大きいと焼結が促進され、粒径や結晶子径が大きくなり過ぎ、サイクル特性の悪化を招く。
［焼成工程］
この焼成工程では、混合工程後のリチウム混合物を、大気雰囲気下又は酸化性雰囲気下で行われる焼成工程に供され、焼成されて焼成物となる。
On the other hand, if the above ratio is larger than 1.30, sintering is promoted, the particle size and crystallite diameter become too large, and the cycle characteristics are deteriorated.
[Baking process]
In this firing step, the lithium mixture after the mixing step is subjected to a firing step performed in an air atmosphere or an oxidizing atmosphere, and fired to obtain a fired product.
焼成の温度は、８００〜１０００℃が好ましく、９００〜１０００℃がより好ましい。８００℃未満になると、反応性が低下して、得られた焼成物において、未反応の余剰リチウムの増加や、結晶構造が十分に整わず結晶性悪化などが起こる。このため、後工程で得られる正極活物質自体から、必要なリチウムが溶出し易くなったりするため、満足出来る電池特性が得られない。一方で、焼成温度が１０００℃より高くなると、リチウム金属複合酸化物の粒子間で激しく焼結が起こり、異常な粒子成長を生じる可能性がある。 The firing temperature is preferably 800 to 1000 ° C, more preferably 900 to 1000 ° C. If the temperature is lower than 800 ° C., the reactivity is lowered, and in the obtained fired product, the amount of unreacted excess lithium increases, the crystal structure is not sufficiently arranged, and the crystallinity deteriorates. For this reason, necessary lithium is easily eluted from the positive electrode active material itself obtained in the subsequent process, so that satisfactory battery characteristics cannot be obtained. On the other hand, when the firing temperature is higher than 1000 ° C., severe sintering occurs between the particles of the lithium metal composite oxide, which may cause abnormal particle growth.
また、焼成時間は、１〜２０時間とすることが好ましく、より好ましくは１０〜１５時間である。１時間未満になると、焼成物の生成が十分に行われないことがあり、好ましくない。一方、２０時間を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。
なお、上記のリチウム混合物は、焼成を行う前に仮焼工程に供せられ、まず、４００〜５５０℃で１〜３時間、仮焼することが好ましく、４５０〜５００℃とすることがより好ましい。
The firing time is preferably 1 to 20 hours, more preferably 10 to 15 hours. If it is less than 1 hour, the fired product may not be sufficiently produced, which is not preferable. On the other hand, even if it exceeds 20 hours, there is no particular problem, but it is not so preferable in consideration of manufacturing cost and efficiency.
The above lithium mixture is subjected to a calcining step before firing, and is preferably calcined at 400 to 550 ° C. for 1 to 3 hours, more preferably 450 to 500 ° C. ..
仮焼工程を経ることで、焼成工程の焼成反応がより穏やかに進み、得られた焼成物の粒子強度を保つと共に、未反応の余剰リチウムの低減や、結晶性向上に繋がる。 By going through the calcining step, the firing reaction in the firing step proceeds more gently, the particle strength of the obtained fired product is maintained, and the amount of unreacted excess lithium is reduced and the crystallinity is improved.
４００℃未満及び５５０℃を超えると、上記の効果を得難くなるため、好ましくない。なお、仮焼の時間は、１〜３時間が好ましい。１時間未満になると、上記の効果を得難くなるため、好ましくない。一方で、３時間を超えても、特に問題無いが、製造コストや効率を考慮するなら、あまり好ましくない。 If the temperature is lower than 400 ° C. and higher than 550 ° C., it becomes difficult to obtain the above effects, which is not preferable. The calcining time is preferably 1 to 3 hours. If it is less than 1 hour, it becomes difficult to obtain the above effect, which is not preferable. On the other hand, there is no particular problem even if it exceeds 3 hours, but it is not so preferable in consideration of manufacturing cost and efficiency.
更に、仮焼及び焼成の雰囲気は、大気雰囲気下のほか、酸化性雰囲気下としてもよく、酸素濃度が１８〜１００容量％の雰囲気下とするのが好ましい。
［表面処理工程］
この表面処理工程では、焼成工程で得た焼成物を、重量比で０．５〜１．０の水に投入し、スラリー化して水洗後、濾過、乾燥することで、リチウム金属複合酸化物（正極活物質）を得る。つまり、焼成物の表面に存在する余剰リチウム（水酸化リチウム及び炭酸リチウム）を水洗し、除去することで、電池容量に影響を及ぼすタップ密度が向上するほか、正極作製時のペーストのゲル化を抑制することにも繋がる。
水が重量比で０．５（投入量の半分）未満であると、スラリーの粘度が高過ぎて、均一撹拌が難しくなる。その一方、水が重量比で１．０（投入量と等量）を超えると、焼成物自体から過剰にリチウムが溶出して、正極活物質の性能が悪化してしまうことがある。また、撹拌の時間は、前記スラリーを０．５〜１時間、撹拌することが好ましい。０．５時間より短いと、撹拌が均一にならないことがあり、１時間を超えても、余剰リチウムの除去率は、ある程度で飽和するため、時間を無駄に費やすことになる。
４．１〜３に関する評価
＜試料の分析方法＞
［組成］
組成に関する分析方法は、特に限定されないが、例えば、酸分解−ＩＣＰ（誘導結合プラズマ）発光分光分析法などによる化学分析法から求めることが出来る。
［平均粒径ＭＶ］
平均粒径ＭＶに関する分析方法は、レーザー回折・散乱法を用いて測定した、体積基準分布（平均値）から求めることが出来る。
［Ｆｓｓｓ（Ｆｉｓｈｅｒ−Ｓｕｂ−Ｓｉｅｖｅ−Ｓｉｚｅｒ）平均粒径］
Ｆｓｓｓ平均粒径に関する分析方法は、フィッシャー空気透過法を用いて測定した、粒子充填層全域による圧力損失から求めることが出来る。
［ＢＥＴ比表面積］
ＢＥＴ比表面積に関する分析方法は、ＢＥＴ式による窒素ガス吸着・脱離法を用いて測定した、窒素ガス吸着量から求めることが出来る。
［ブレーン比表面積］
ブレーン比表面積に関する分析方法は、ブレーン空気透過法を用いて測定した、粒子充填層を透過する空気量、時間、圧力差から求めることが出来る。
［ＭＶ／Ｆｓｓｓ］
ＭＶ／Ｆｓｓｓは、上記の平均粒径ＭＶ及びＦｓｓｓ平均粒径から求めることができ、０．６０〜１．８０が好ましく、０．７０〜１．７０がより好ましい。
［ＢＥＴ／ブレーン］
ＢＥＴ／ブレーンは、上記のＢＥＴ比表面積及びブレーン比表面積から求めることができ、０．６０〜１．７０が好ましく、０．７０〜１．５０がより好ましい。
［微細粒子含有量］
１μｍ以下の微細粒子含有量に関する分析方法は、レーザー回折・散乱法を用いて測定した、体積基準分布（累積値）から求めることが出来る。なお、１μｍ以下の微細粒子含有量は、０．１５質量％未満であることが好ましく、０．１０質量％未満であることがより好ましい。
［タップ密度］
タップ密度に関する分析方法は、ＪＩＳ−Ｚ−２５０４に基づいた振とう比重測定器を用いて測定した、嵩密度から求めることが出来る。なお、タップ密度は、１．５０〜３．００ｇ／ｃｍ３が好ましく、１．６０〜２．９０ｇ／ｃｍ３がより好ましい。
Further, the atmosphere of calcining and firing may be an oxidizing atmosphere as well as an atmospheric atmosphere, and is preferably an atmosphere having an oxygen concentration of 18 to 100% by volume.
[Surface treatment process]
In this surface treatment step, the fired product obtained in the firing step is put into water having a weight ratio of 0.5 to 1.0, slurried, washed with water, filtered, and dried to obtain a lithium metal composite oxide ( Positive positive active material) is obtained. In other words, by washing and removing excess lithium (lithium hydroxide and lithium carbonate) existing on the surface of the fired product, the tap density that affects the battery capacity is improved, and the paste is gelled during the production of the positive electrode. It also leads to suppression.
If the weight ratio of water is less than 0.5 (half the input amount), the viscosity of the slurry is too high and uniform stirring becomes difficult. On the other hand, if the weight ratio of water exceeds 1.0 (equal to the input amount), lithium may be excessively eluted from the fired product itself, and the performance of the positive electrode active material may deteriorate. The stirring time is preferably 0.5 to 1 hour for the slurry. If it is shorter than 0.5 hours, the stirring may not be uniform, and even if it exceeds 1 hour, the removal rate of excess lithium is saturated to some extent, so that time is wasted.
Evaluation of 4.1 to 3 <Sample analysis method>
[composition]
The analysis method regarding the composition is not particularly limited, but can be obtained from, for example, a chemical analysis method such as acid decomposition-ICP (inductively coupled plasma) emission spectroscopy.
[Average particle size MV]
The analysis method for the average particle size MV can be obtained from the volume reference distribution (average value) measured by using the laser diffraction / scattering method.
[Fsss (Fisher-Sub-Sieve-Sizer) average particle size]
The analysis method for the Fsss average particle size can be obtained from the pressure loss over the entire particle-filled layer measured by the Fisher air permeation method.
[BET specific surface area]
The analysis method for the BET specific surface area can be obtained from the amount of nitrogen gas adsorbed measured by using the nitrogen gas adsorption / desorption method by the BET method.
[Brain specific surface area]
The analysis method for the brain specific surface area can be obtained from the amount of air passing through the particle-filled layer, the time, and the pressure difference measured by the brain air permeation method.
[MV / Fsss]
The MV / Fsss can be obtained from the above average particle size MV and Fsss average particle size, and is preferably 0.60 to 1.80, more preferably 0.70 to 1.70.
[BET / Brain]
The BET / brain can be determined from the above-mentioned BET specific surface area and brain specific surface area, and is preferably 0.60 to 1.70, more preferably 0.70 to 1.50.
[Fine particle content]
The analysis method for the fine particle content of 1 μm or less can be obtained from the volume reference distribution (cumulative value) measured by the laser diffraction / scattering method. The fine particle content of 1 μm or less is preferably less than 0.15% by mass, more preferably less than 0.10% by mass.
[Tap density]
The analysis method regarding the tap density can be obtained from the bulk density measured by using a shaking specific gravity measuring device based on JIS-Z-2504. Incidentally, the tap density is preferably 1.50~3.00g / cm 3, 1.60~2.90g / cm 3 is more preferable.
以下の通り、実施例及び比較例をそれぞれ挙げ、本発明について、より詳細に説明するが、本発明は、記載した実施例の内容に、何ら限定されるものではない。
以下、実施例を用いて本発明を更に説明する。
The present invention will be described in more detail with reference to Examples and Comparative Examples, respectively, but the present invention is not limited to the contents of the described Examples.
Hereinafter, the present invention will be further described with reference to Examples.
［乾燥物（前駆体）の製造］
＜晶析工程＞
まず、遠心式撹拌機、オーバーフローパイプ、不活性ガス供給ノズルなどを備えた、ステンレス製の円筒型３４Ｌ反応槽に水を３０Ｌ供給した後、ｐＨ（２５℃基準）が１３．５となるまで水酸化ナトリウム溶液（２５質量％）を加え、反応槽内の温度を４０℃に保持し、一定速度で撹拌することにより、反応溶液を作製した。撹拌には、遠心式撹拌機であるＣ−Ｍｉｘ（シーミックス）ＤＡＨ００５Ａ（株式会社アクアテックス製）を用いた。それと同時に、反応槽内に窒素ガスを導入し、気相部を酸素濃度が１．０容量％以下の非酸化性雰囲気に制御した。
[Manufacturing of dried product (precursor)]
<Crystalization process>
First, 30 L of water is supplied to a cylindrical 34 L reaction tank made of stainless steel equipped with a centrifugal stirrer, an overflow pipe, an inert gas supply nozzle, etc., and then water is supplied until the pH (25 ° C. standard) reaches 13.5. A reaction solution was prepared by adding a sodium oxide solution (25% by mass), maintaining the temperature in the reaction vessel at 40 ° C., and stirring at a constant rate. For stirring, a centrifugal stirrer C-Mix DAH005A (manufactured by Aquatex Co., Ltd.) was used. At the same time, nitrogen gas was introduced into the reaction vessel to control the gas phase portion to a non-oxidizing atmosphere having an oxygen concentration of 1.0% by volume or less.
次に、硫酸ニッケル六水和物、硫酸マンガン一水和物、硫酸コバルト七水和物を、ニッケル、マンガン、コバルトのモル比が、Ｎｉ：Ｍｎ：Ｃｏ＝３５：３０：３５で、ニッケル、マンガン、コバルトの濃度が、合計２ｍｏｌ／Ｌとなる様に、水に溶解して原料溶液を作製した。この原料溶液を、上記反応溶液に０．３Ｌ／分で加え、それと共にアンモニア水（２５質量％）及び水酸化ナトリウム溶液（２５質量％）溶液も、反応溶液に一定速度で加えて、反応溶液中のアンモニウムイオン（ＮＨ４ ＋）濃度を１０ｇ／Ｌに保持した状態で、ｐＨ（２５℃基準）を１３．５に制御した。
また、反応溶液のｐＨ（２５℃基準）及びアンモニウムイオン（ＮＨ４ ＋）濃度は、予め反応槽に設置したｐＨ／アンモニア測定キット（ｐＨ計及びアンモニウムイオンメーターの複合機）である、Ｏｒｉｏｎ−Ｓｔａｒ−Ａ２１４（サーモフィッシャーサイエンティフィック株式会社製）により、それぞれ測定した。
反応が安定し、反応槽内が定常状態となった時点から、この条件で、晶析処理を４時間行い、４時間経過後、反応槽のオーバーフローパイプから連続的に採取した水酸化物（乾燥状態で、約８．３ｋｇ）について、組成を評価したところ、一般式：Ｎｉ０.３５Ｍｎ０.３０Ｃｏ０.３５（ＯＨ）２で表される、ニッケルマンガンコバルト複合水酸化物が得られていることを確認した。なお、組成の評価は、得られた水酸化物を乾燥試料とした後、後述の分析方法に従って実施した。
＜濾過工程＞
上記の水酸化物に対して、フィルタープレス濾過機であるＴＫ−４０８（住友金属鉱山エンジニアリング株式会社製）を用いた固液分離操作を行った。
Next, nickel sulfate hexahydrate, manganese sulfate monohydrate, and cobalt sulfate heptahydrate were added to nickel, manganese, and cobalt with a molar ratio of Ni: Mn: Co = 35:30:35. A raw material solution was prepared by dissolving in water so that the total concentration of manganese and cobalt was 2 mol / L. This raw material solution is added to the above reaction solution at 0.3 L / min, and a solution of aqueous ammonia (25% by mass) and sodium hydroxide solution (25% by mass) is also added to the reaction solution at a constant rate to prepare the reaction solution. the ammonium ion (NH 4 +) concentration in while maintaining the 10 g / L, was controlled pH the (25 ° C. basis) 13.5.
Further, pH (25 ° C. basis) and ammonium ion (NH 4 +) concentration of the reaction solution is pre-reactor installation the pH / ammonia assay kit (MFP pH meter and ammonium ion meter), Orion-Star -A214 (manufactured by Thermo Fisher Scientific Co., Ltd.) was used for each measurement.
From the time when the reaction became stable and the inside of the reaction vessel became a steady state, the crystallization treatment was carried out under these conditions for 4 hours, and after 4 hours, the hydroxide continuously collected from the overflow pipe of the reaction vessel (drying). When the composition was evaluated for about 8.3 kg) in this state, a nickel-manganese-cobalt composite hydroxide represented by the general formula: Ni 0.35 Mn 0.30 Co 0.35 (OH) 2 was obtained. I confirmed that. The composition was evaluated by using the obtained hydroxide as a dry sample and then following the analysis method described later.
<Filtration process>
The above hydroxide was subjected to a solid-liquid separation operation using a filter press filter TK-408 (manufactured by Sumitomo Metal Mining Engineering Co., Ltd.).
固液分離操作の後、水酸化ナトリウム溶液（０．１ｍｏｌ／Ｌ）を洗浄液として、その５０Ｌをフィルタープレス濾過機に通液することで不純物を除去し、その後、更に洗浄液の２倍量のイオン交換水を通液し、水洗することで含水澱物を得た。
＜乾燥工程＞
濾過工程で得た含水澱物を、２００℃で５時間乾燥して乾燥物（前駆体）を得た。
［酸化焙焼物（中間物）の製造］
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、４００℃で１時間仮焼し、その後、８００℃で１時間酸化焙焼することで、一般式：Ｎｉ０.３５Ｍｎ０.３０Ｃｏ０.３５Ｏで表される、酸化焙焼物（中間物）を得た。なお、酸化焙焼物の組成の評価は、後述の分析方法に従って実施した。
［リチウム金属複合酸化物（正極活物質）の製造］
＜混合工程＞
酸化焙焼工程で得た酸化焙焼物と、リチウム化合物である水酸化リチウムとを混合し、リチウム混合物を得た。ここで、リチウム化合物は、酸化焙焼物に対して、Ｌｉ／Ｍｅ＝１．０１となる様に秤量し、混合には、シェーカミキサ装置であるＴＵＲＢＵＬＡ−ＴｙｐｅＴ２Ｃ（ウィリー・エ・バッコーフェン（ＷＡＢ）社製）を用いた。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、５５０℃で３時間仮焼し、その後、１０００℃で２０時間焼成することで、焼成物を作製した。
＜表面処理工程＞
焼成工程で得た焼成物に、重量比で０．８の水を加えスラリー化し、撹拌することで水洗した後、濾過及び乾燥を行い、一般式：Ｌｉ１．０１Ｎｉ０.３５Ｍｎ０.３０Ｃｏ０.３５Ｏ２で表される、リチウムニッケルマンガンコバルト複合酸化物（正極活物質）を得た。なお、リチウムニッケルマンガンコバルト複合酸化物の組成、平均粒径ＭＶ、Ｆｓｓｓ平均粒径、ＢＥＴ比表面積、ブレーン比表面積、タップ密度の評価は、後述の分析方法に従って実施した。
［各工程での評価］
＜分析方法＞
各工程で採取した試料の分析方法は、以下の通りである。
（１）組成
組成は、試料を酸分解−ＩＣＰ法により分析し、試料を無機酸で加熱分解処理することで分析検体液が得られ、これをマルチ型ＩＣＰ発光分光分析装置であるＩＣＰＥ−９０００（株式会社島津製作所製）を用いて測定した。
（２）平均粒径ＭＶ
平均粒径ＭＶは、試料をレーザー回折・散乱法により分析し、体積基準分布（平均値）から求めた。なお、測定には、レーザー回折・散乱方式で、かつ、超音波発生器内臓型の粒度分布測定装置であるマイクロトラックＭＴ３３００ＥＸ−２（マイクロトラック・ベル株式会社製）を用いた。
（３）Ｆｓｓｓ平均粒径
Ｆｓｓｓ平均粒径は、試料をフィッシャー空気透過法により分析し、粒子充填層全域による圧力損失から求めた。なお、測定には、全自動乾式粒子径測定装置であるＳｕｂｓｉｅｖｅ−Ａｕｔｏ−Ｓｉｚｅｒ（ＳＡＳ）（マイクロメリティックスジャパン合同会社製）を用いた。
（４）ＢＥＴ比表面積
ＢＥＴ比表面積は、試料をＢＥＴ式による窒素ガス吸着・脱離法により分析し、窒素ガス吸着量から求めた。なお、測定には、流動方式で、かつ、窒素ガス吸着法の比表面積測定装置であるマックソーブ１２００シリーズ（株式会社マウンテック製）を用いた。
（５）ブレーン比表面積
ブレーン比表面積は、試料をブレーン空気透過法により分析し、粒子充填層を透過する空気量、時間、圧力差から求めた。なお、測定には、ブレーン空気透過装置・粉末度測定器（筒井理化学器械株式会社製）を用いた。
（６）ＭＶ／Ｆｓｓｓ
ＭＶ／Ｆｓｓｓは、上記の平均粒径ＭＶ及びＦｓｓｓ平均粒径から求めた。
（７）ＢＥＴ／ブレーン
ＢＥＴ／ブレーンは、上記のＢＥＴ比表面積及びブレーン比表面積から求めた。
（８）微細粒子含有量
１μｍ以下の微細粒子の含有量は、試料をレーザー回折・散乱法により分析し、体積基準分布（累積値）から求めた。なお、測定には、レーザー回折・散乱方式で、かつ、超音波発生器内臓型の粒度分布測定装置であるマイクロトラックＭＴ３３００ＥＸ−２（マイクロトラック・ベル株式会社製）を用いた。
（９）タップ密度
タップ密度は、試料をＪＩＳ−Ｚ−２５０４に基づいた振とう比重測定器により分析し、試料を２０ｍｌメスシリンダーに充填後、このメスシリンダーについて、高さ２ｃｍからの自由落下を５００回繰り返す方法で、密に充填させてから測定した。なお、測定には、振とう比重測定器であるＫＲＳ−４０９（株式会社蔵持科学器械製作所製）を用いた。
After the solid-liquid separation operation, impurities are removed by using a sodium hydroxide solution (0.1 mol / L) as a cleaning solution and passing 50 L of the solution through a filter press filter, and then further twice the amount of ions as the cleaning solution. A hydrous starch was obtained by passing the exchanged water through and washing with water.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 200 ° C. for 5 hours to obtain a dried product (precursor).
[Manufacturing of oxidized roasted food (intermediate)]
<Oxidation roasting process>
Was obtained in the drying step dry matter, first, 1 hour calcination at 400 ° C., then, by 1 hour oxidation roasting at 800 ° C., the general formula: Ni 0.35 Mn 0.30 Co 0.35 O An oxidized roasted product (intermediate) represented by. The composition of the oxidized roasted product was evaluated according to the analysis method described later.
[Manufacturing of lithium metal composite oxide (positive electrode active material)]
<Mixing process>
The oxidative roasted product obtained in the oxidative roasting step was mixed with lithium hydroxide, which is a lithium compound, to obtain a lithium mixture. Here, the lithium compound is weighed so that Li / Me = 1.01 with respect to the oxidized roasted product, and for mixing, TURBULA-TypeT2C (manufactured by Willie et Bacoffen (WAB)), which is a shake mixer device, is used. ) Was used.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 550 ° C. for 3 hours and then calcined at 1000 ° C. for 20 hours to prepare a calcined product.
<Surface treatment process>
Water of 0.8 by weight is added to the calcined product obtained in the calcining step to form a slurry, which is washed with water by stirring, then filtered and dried. General formula: Li 1.01 Ni 0.35 Mn 0. A lithium nickel-manganese-cobalt composite oxide (positive electrode active material) represented by 30 Co 0.35 O 2 was obtained. The composition of the lithium nickel-manganese-cobalt composite oxide, the average particle size MV, the Fsss average particle size, the BET specific surface area, the brain specific surface area, and the tap density were evaluated according to the analysis method described later.
[Evaluation in each process]
<Analysis method>
The analysis method of the sample collected in each step is as follows.
(1) Composition The composition is obtained by analyzing the sample by the acid decomposition-ICP method and heat-decomposing the sample with an inorganic acid to obtain an analytical sample solution, which is ICPE-9000, which is a multi-type ICP emission spectroscopic analyzer. Measured using (manufactured by Shimadzu Corporation).
(2) Average particle size MV
The average particle size MV was determined from the volume reference distribution (mean value) by analyzing the sample by the laser diffraction / scattering method. For the measurement, a laser diffraction / scattering method and a particle size distribution measuring device with a built-in ultrasonic generator, Microtrack MT3300EX-2 (manufactured by Microtrack Bell Co., Ltd.) was used.
(3) Fss average particle size The Fsss average particle size was determined from the pressure loss over the entire particle-filled layer by analyzing the sample by the Fisher air permeation method. For the measurement, a fully automatic dry particle size measuring device, Subsieve-Auto-Sizer (SAS) (manufactured by Micromeritix Japan GK) was used.
(4) BET Specific Surface Area The BET specific surface area was determined from the amount of nitrogen gas adsorbed by analyzing the sample by the nitrogen gas adsorption / desorption method by the BET method. For the measurement, a MacSorb 1200 series (manufactured by Mountech Co., Ltd.), which is a flow method and a specific surface area measuring device of the nitrogen gas adsorption method, was used.
(5) Blaine specific surface area The Blaine specific surface area was determined from the amount of air passing through the particle-filled layer, the time, and the pressure difference by analyzing the sample by the brain air permeation method. A brain air permeation device / powder degree measuring device (manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) was used for the measurement.
(6) MV / Fsss
MV / Fsss was determined from the above average particle size MV and Fsss average particle size.
(7) BET / Brain BET / Brain was determined from the above BET specific surface area and Brain specific surface area.
(8) Fine particle content The content of fine particles of 1 μm or less was determined from the volume reference distribution (cumulative value) by analyzing the sample by a laser diffraction / scattering method. For the measurement, a laser diffraction / scattering method and a particle size distribution measuring device with a built-in ultrasonic generator, Microtrack MT3300EX-2 (manufactured by Microtrack Bell Co., Ltd.) was used.
(9) Tap Density The tap density is determined by analyzing the sample with a shaking specific gravity measuring device based on JIS-Z-2504, filling the sample in a 20 ml graduated cylinder, and then freely dropping the sample from a height of 2 cm. It was measured after being densely filled by a method of repeating 500 times. For the measurement, KRS-409 (manufactured by Kuramochi Kagaku Kikai Seisakusho Co., Ltd.), which is a shaking specific gravity measuring instrument, was used.
以下の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
反応槽内の温度を４５℃、ｐＨ（２５℃基準）を１３．０に制御した。
＜乾燥工程＞
濾過工程で得た含水澱物を、２００℃で３時間乾燥した。
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、４００℃で３時間仮焼し、その後、８００℃で３時間酸化焙焼した。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、５５０℃で２時間仮焼し、その後、１０００℃で１５時間焼成した。
The procedure was the same as in Example 1 except for the following conditions.
<Crystalization process>
The temperature in the reaction vessel was controlled to 45 ° C., and the pH (based on 25 ° C.) was controlled to 13.0.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 200 ° C. for 3 hours.
<Oxidation roasting process>
The dried product obtained in the drying step was first calcined at 400 ° C. for 3 hours, and then oxidatively roasted at 800 ° C. for 3 hours.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 550 ° C. for 2 hours and then at 1000 ° C. for 15 hours.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。 The analysis results of the samples collected in each step are as shown in Table 1.
以下の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
反応槽内の温度を５０℃、ｐＨ（２５℃基準）を１２．５に制御した。
＜乾燥工程＞
濾過工程で得た含水澱物を、１５０℃で５時間乾燥した。
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、５００℃で３時間仮焼し、その後、９００℃で３時間酸化焙焼した。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、５００℃で２時間仮焼し、その後、９００℃で１０時間焼成した。
The procedure was the same as in Example 1 except for the following conditions.
<Crystalization process>
The temperature in the reaction vessel was controlled to 50 ° C., and the pH (based on 25 ° C.) was controlled to 12.5.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 150 ° C. for 5 hours.
<Oxidation roasting process>
The dried product obtained in the drying step was first calcined at 500 ° C. for 3 hours, and then oxidatively roasted at 900 ° C. for 3 hours.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 500 ° C. for 2 hours and then calcined at 900 ° C. for 10 hours.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。 The analysis results of the samples collected in each step are as shown in Table 1.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
反応槽内の温度を５５℃、ｐＨ（２５℃基準）を１２．０に制御した。
＜乾燥工程＞
濾過工程で得た含水澱物を、１００℃で３時間乾燥した。
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、５５０℃で１時間仮焼し、その後、１０００℃で３時間酸化焙焼した。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、４００℃で３時間仮焼し、その後、８００℃で５時間焼成した。
The procedure was the same as in Example 1 except for the following conditions.
<Crystalization process>
The temperature in the reaction vessel was controlled to 55 ° C., and the pH (based on 25 ° C.) was controlled to 12.0.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 100 ° C. for 3 hours.
<Oxidation roasting process>
The dried product obtained in the drying step was first calcined at 550 ° C. for 1 hour, and then oxidatively roasted at 1000 ° C. for 3 hours.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 400 ° C. for 3 hours and then calcined at 800 ° C. for 5 hours.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。 The analysis results of the samples collected in each step are as shown in Table 1.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
反応槽内の温度を６０℃、ｐＨ（２５℃基準）を１１．０に制御した。
＜乾燥工程＞
濾過工程で得た含水澱物を、１００℃で３時間乾燥した。
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、５５０℃で１時間仮焼し、その後、１０００℃で３時間酸化焙焼した。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、４００℃で３時間仮焼し、その後、８００℃で５時間焼成した。
The procedure was the same as in Example 1 except for the following conditions.
<Crystalization process>
The temperature in the reaction vessel was controlled to 60 ° C., and the pH (based on 25 ° C.) was controlled to 11.0.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 100 ° C. for 3 hours.
<Oxidation roasting process>
The dried product obtained in the drying step was first calcined at 550 ° C. for 1 hour, and then oxidatively roasted at 1000 ° C. for 3 hours.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 400 ° C. for 3 hours and then calcined at 800 ° C. for 5 hours.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。 The analysis results of the samples collected in each step are as shown in Table 1.
下記の条件以外は、実施例１と同様の手順を行った。
＜晶析工程＞
反応槽内の温度を６０℃、ｐＨ（２５℃基準）を１０．５に制御した。
＜乾燥工程＞
濾過工程で得た含水澱物を、１００℃で３時間乾燥した。
＜酸化焙焼工程＞
乾燥工程で得た乾燥物を、まず、５５０℃で１時間仮焼し、その後、１０００℃で３時間酸化焙焼した。
＜焼成工程＞
混合工程で得たリチウム混合物を、まず、４００℃で３時間仮焼し、その後、８００℃で５時間焼成した。
The procedure was the same as in Example 1 except for the following conditions.
<Crystalization process>
The temperature in the reaction vessel was controlled to 60 ° C., and the pH (based on 25 ° C.) was controlled to 10.5.
<Drying process>
The hydrous starch obtained in the filtration step was dried at 100 ° C. for 3 hours.
<Oxidation roasting process>
The dried product obtained in the drying step was first calcined at 550 ° C. for 1 hour, and then oxidatively roasted at 1000 ° C. for 3 hours.
<Baking process>
The lithium mixture obtained in the mixing step was first calcined at 400 ° C. for 3 hours and then calcined at 800 ° C. for 5 hours.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。
[比較例１]
以下の条件以外は、実施例２と同様の手順を行った。
＜晶析工程＞
撹拌には、羽根式撹拌機であるポータブルミキサーＡ７２０（佐竹化学機械工業株式会社製）を用いた。
The analysis results of the samples collected in each step are as shown in Table 1.
[Comparative Example 1]
The procedure was the same as in Example 2 except for the following conditions.
<Crystalization process>
For stirring, a portable mixer A720 (manufactured by Satake Chemical Machinery Co., Ltd.), which is a blade type stirrer, was used.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。
[比較例２]
下記の条件以外は、実施例４と同様の手順を行った。
＜晶析工程＞
撹拌には、上記の羽根式撹拌機を用いた。
The analysis results of the samples collected in each step are as shown in Table 1.
[Comparative Example 2]
The procedure was the same as in Example 4 except for the following conditions.
<Crystalization process>
The above-mentioned blade type stirrer was used for stirring.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。
[比較例３]
下記の条件以外は、実施例５と同様の手順を行った。
＜晶析工程＞
撹拌には、上記の羽根式撹拌機を用いた。
The analysis results of the samples collected in each step are as shown in Table 1.
[Comparative Example 3]
The procedure was the same as in Example 5 except for the following conditions.
<Crystalization process>
The above-mentioned blade type stirrer was used for stirring.
また、各工程において採取した試料の分析結果は、表１に記載の通りであった。 The analysis results of the samples collected in each step are as shown in Table 1.
表１に示した通り、実施例１〜６では、レーザー回折散乱法による平均粒径ＭＶと、フィッシャー空気透過法によるＦｓｓｓ平均粒径の比であるＭＶ／Ｆｓｓｓが、０．６０〜１．８０であり、ガス吸着法によるＢＥＴ比表面積と、ブレーン空気透過法によるブレーン比表面積の比であるＢＥＴ／ブレーンが、０．６０〜１．６０であり、どちらも最適な範囲であった。また、１μｍ以下の微細粒子含有量が、０．１５質量％未満であり、タップ密度が１．５０〜３．００ｇ／ｃｍ３であった。これらの評価結果から、実施例１〜６では、特性が非常に安定したリチウム金属複合酸化物粒子が得られていることが分かった。
これに対して、比較例１〜３では、上記のＭＶ／Ｆｓｓｓ及びＢＥＴ／ブレーンが、どちらも最適な範囲から外れており、かつ、１μｍ以下の微細粒子が、０．１５質量％以上含まれていたことから、実施例１〜６の様に、特性が安定したリチウム金属複合酸化物粒子は得られなかった。
As shown in Table 1, in Examples 1 to 6, the MV / Fsss, which is the ratio of the average particle size MV obtained by the laser diffraction / scattering method and the Fsss average particle size obtained by the Fisher air permeation method, is 0.60 to 1.80. The BET / brain, which is the ratio of the BET specific surface area by the gas adsorption method to the brain specific surface area by the brain air permeation method, was 0.60 to 1.60, both of which were in the optimum range. The fine particle content of 1 μm or less was less than 0.15% by mass, and the tap density was 1.50 to 3.00 g / cm 3 . From these evaluation results, it was found that in Examples 1 to 6, lithium metal composite oxide particles having very stable characteristics were obtained.
On the other hand, in Comparative Examples 1 to 3, both the above MV / Fsss and BET / brain are out of the optimum range, and fine particles of 1 μm or less are contained in an amount of 0.15% by mass or more. Therefore, unlike Examples 1 to 6, lithium metal composite oxide particles having stable characteristics could not be obtained.
Claims (4)
（式中、ｓ、ｘ、ｙ及びαは、それぞれ０．９５≦ｓ≦１．３０、０．０５≦ｘ≦０．３５、０≦ｙ≦０．４５及び０≦α≦０．２を満たす数、Ｍは、Ｍｎ、Ａｌ、Ｗ、Ｍｏ、Ｎｂからなる群より選ばれた、少なくとも１種の金属元素を示す）で表されることを特徴とする請求項１又は２にリチウムイオン二次電池用正極活物質。 Formula: Li s Ni 1-x- y Co x M y O 2 + α
(In the formula, s, x, y and α have 0.95 ≦ s ≦ 1.30, 0.05 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.45 and 0 ≦ α ≦ 0.2, respectively. The number to be satisfied, M, represents at least one metal element selected from the group consisting of Mn, Al, W, Mo, and Nb). Lithium ion 2 according to claim 1 or 2. Positive electrode active material for next battery.
A crystal obtained by mixing a solution containing a transition metal element, a solution containing a typical metal element, a solution containing a transition metal or a typical metal element, an alkali, and ammonium ions to obtain a slurry containing a metal composite hydroxide. A method for producing a positive electrode active material for a lithium ion secondary battery, which comprises an analysis step and uses a centrifugal stirrer for the mixing.
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| JPH029722A (en) * | 1988-06-29 | 1990-01-12 | Mitsui Mining & Smelting Co Ltd | Production of manganese oxide powder |
| JPH07104522A (en) * | 1993-10-01 | 1995-04-21 | Powder Tec Kk | Resin coated carrier for electrophotographic developer, its production and developer using the same |
| JP2004363097A (en) * | 2003-05-15 | 2004-12-24 | Nichia Chem Ind Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| JP2005222851A (en) * | 2004-02-06 | 2005-08-18 | Sii Micro Parts Ltd | Electrode active material and electrochemical cell using it |
| JP2019116411A (en) * | 2017-12-27 | 2019-07-18 | 住友金属鉱山株式会社 | Manufacturing method of nickel-containing hydroxide |
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| JPH029722A (en) * | 1988-06-29 | 1990-01-12 | Mitsui Mining & Smelting Co Ltd | Production of manganese oxide powder |
| JPH07104522A (en) * | 1993-10-01 | 1995-04-21 | Powder Tec Kk | Resin coated carrier for electrophotographic developer, its production and developer using the same |
| JP2004363097A (en) * | 2003-05-15 | 2004-12-24 | Nichia Chem Ind Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| JP2005222851A (en) * | 2004-02-06 | 2005-08-18 | Sii Micro Parts Ltd | Electrode active material and electrochemical cell using it |
| JP2019116411A (en) * | 2017-12-27 | 2019-07-18 | 住友金属鉱山株式会社 | Manufacturing method of nickel-containing hydroxide |
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