JP2018073563A - Positive electrode material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery arranged by use thereof, and method for manufacturing positive electrode material for nonaqueous electrolyte secondary battery - Google Patents
Positive electrode material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery arranged by use thereof, and method for manufacturing positive electrode material for nonaqueous electrolyte secondary battery Download PDFInfo
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- JP2018073563A JP2018073563A JP2016210152A JP2016210152A JP2018073563A JP 2018073563 A JP2018073563 A JP 2018073563A JP 2016210152 A JP2016210152 A JP 2016210152A JP 2016210152 A JP2016210152 A JP 2016210152A JP 2018073563 A JP2018073563 A JP 2018073563A
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- secondary battery
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 120
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title description 12
- 239000000843 powder Substances 0.000 claims abstract description 84
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 76
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002905 metal composite material Substances 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 230000002776 aggregation Effects 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 238000005054 agglomeration Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims 2
- 239000011163 secondary particle Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 229910015032 LiNiCoMO Inorganic materials 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 239000002131 composite material Substances 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
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- 239000003792 electrolyte Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 4
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- 239000011572 manganese Substances 0.000 description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-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
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- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229910006798 Li1.02Ni0.82Co0.15Al0.03O2 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
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- 239000006182 cathode active material Substances 0.000 description 1
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- 150000005678 chain carbonates Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 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 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水系電解質二次電池用正極材料、該正極材料を用いた非水系電解質二次電池、および非水系電解質二次電池用正極材料の製造方法に関する。 The present invention relates to a positive electrode material for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery using the positive electrode material, and a method for producing a positive electrode material for a non-aqueous electrolyte secondary battery.
近年、携帯電話やノート型パソコンなどの携帯電子機器の普及に伴い、高いエネルギー密度を有する小型で軽量な非水系電解質二次電池の開発が強く望まれ、また、ハイブリット自動車をはじめとする電気自動車用の電池として高出力の二次電池の開発も強く望まれている。このような要求を満たす二次電池として、リチウムイオン二次電池がある。 In recent years, with the widespread use of portable electronic devices such as mobile phones and notebook computers, development of small and lightweight non-aqueous electrolyte secondary batteries with high energy density is strongly desired, and electric vehicles including hybrid vehicles Development of a high-power secondary battery as a battery for power generation is also strongly desired. As a secondary battery satisfying such requirements, there is a lithium ion secondary battery.
このリチウムイオン二次電池は、負極および正極の活物質に、リチウムが脱離および挿入できる材料が用いられている。このようなリチウムイオン二次電池については、現在研究、開発が盛んに行われているところであるが、中でも、層状またはスピネル型のリチウム金属複合酸化物を正極材料に用いたリチウムイオン二次電池は、４Ｖ級の高い電圧が得られるため、高いエネルギー密度を有する電池として実用化が進んでいる。 In this lithium ion secondary battery, a material from which lithium can be desorbed and inserted is used for the active material of the negative electrode and the positive electrode. Such lithium ion secondary batteries are currently being actively researched and developed. Among them, lithium ion secondary batteries using a layered or spinel type lithium metal composite oxide as a positive electrode material are among them. Since a high voltage of 4V class can be obtained, practical use is progressing as a battery having a high energy density.
これまでに提案されている活物質材料としては、合成が比較的容易なリチウムコバルト複合酸化物（ＬｉＣｏＯ２）や、コバルトよりも安価なニッケルを用いたリチウムニッケル複合酸化物（ＬｉＮｉＯ２）、リチウムニッケルコバルトマンガン複合酸化物（ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２）、マンガンを用いたリチウムマンガン複合酸化物（ＬｉＭｎ２Ｏ４）などが挙げられる。このうちリチウムニッケル複合酸化物、及びリチウムニッケルコバルトマンガン複合酸化物は、サイクル特性が良く、低抵抗で高出力が得られ電池特性に優れた材料として注目され、近年さらには高出力化に必要な低抵抗化が重要視されている。 Examples of active material materials that have been proposed so far include lithium cobalt composite oxide (LiCoO 2 ) that is relatively easy to synthesize, lithium nickel composite oxide (LiNiO 2 ) using nickel that is less expensive than cobalt, lithium Examples thereof include nickel cobalt manganese composite oxide (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ), lithium manganese composite oxide (LiMn 2 O 4 ) using manganese, and the like. Among these, lithium nickel composite oxide and lithium nickel cobalt manganese composite oxide are attracting attention as materials having good cycle characteristics, low resistance and high output, and excellent battery characteristics. In recent years, they are required for higher output. Low resistance is regarded as important.
上記の活物質材料に対して、さらなる低抵抗化を実現する方法としては、リチウムイオン伝導性物質を、活物質材料に被覆する手法が用いられており、とりわけ、タングステン酸リチウムやケイ酸リチウムなどが有用とされ、他の金属元素についても研究が進んでいる。 As a method for further reducing the resistance of the above active material, a method of coating a lithium ion conductive material on the active material is used, and in particular, lithium tungstate, lithium silicate, etc. Is also useful, and research is also progressing on other metal elements.
ここで、特許文献１では、リチウムコバルト系複合酸化物に、Ｚｒ等の１種類の金属元素と酸素元素と、のみからなる金属酸化物を被覆することで放電容量やエネルギー密度などの負荷特性、サイクル特性、安全性に優れた二次電池について述べられている。しかし、特許文献１では、特許文献１の発明に関する部分に金属元素のランタンの記載はなく、加えて、金属酸化物の被膜により高出力化を達成できるとする記載はない。 Here, in Patent Document 1, load characteristics such as discharge capacity and energy density are obtained by coating a lithium cobalt based composite oxide with a metal oxide composed of only one kind of metal element such as Zr and oxygen element. A secondary battery having excellent cycle characteristics and safety is described. However, in Patent Document 1, there is no description of metal element lanthanum in the portion related to the invention of Patent Document 1, and there is no description that high output can be achieved by a metal oxide film.
また、特許文献２は、コバルト酸リチウム粒子の表面に、Ｚｒ化合物を局在させることにより、二次電池に用いたときに負荷特性や、サイクル特性に優れ、さらには高温高電圧で安定となるコバルト酸リチウムが開示されている。さらに、コバルト酸リチウムを製造する方法として、酸化コバルトであるコバルト原料と、酸化ジルコニウムであるジルコニウム原料と、炭酸リチウムであるリチウム原料を混合、焼成し、一気にコバルト酸リチウム粒子を製造していることが、特許文献２では開示されている。しかし、本文献も、金属元素のランタンの記載がなく、加えて、Ｚｒ化合物を局在させることで高出力化を達成できるとする記載はない。 Patent Document 2 discloses that a Zr compound is localized on the surface of lithium cobalt oxide particles, so that it is excellent in load characteristics and cycle characteristics when used in a secondary battery, and is stable at high temperature and high voltage. Lithium cobaltate is disclosed. Furthermore, as a method for producing lithium cobalt oxide, a cobalt raw material that is cobalt oxide, a zirconium raw material that is zirconium oxide, and a lithium raw material that is lithium carbonate are mixed and fired to produce lithium cobalt oxide particles all at once. However, this is disclosed in Patent Document 2. However, this document also does not describe lanthanum, which is a metal element. In addition, there is no description that high output can be achieved by localizing a Zr compound.
本発明は係る問題点に鑑み、正極に用いられた場合に高容量の低下を抑制しながら高出力が得られる非水系電解質二次電池用正極材料を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a positive electrode material for a non-aqueous electrolyte secondary battery that can obtain a high output while suppressing a decrease in high capacity when used in a positive electrode.
本発明者らは、上記課題を解決するため、非水系電解質二次電池用正極活物質として用いられるリチウム金属複合酸化物の粉体特性および電池の正極抵抗に対する影響について鋭意研究したところ、リチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、を単に混合することで、電池の正極抵抗を大幅に低減して出力特性を向上させることが可能であることを見出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have intensively studied the influence of the lithium metal composite oxide used as the positive electrode active material for the non-aqueous electrolyte secondary battery on the powder characteristics and the positive electrode resistance of the battery. It has been found that by simply mixing the composite oxide powder and the lithium lanthanum zirconate powder, it is possible to significantly reduce the positive electrode resistance of the battery and improve the output characteristics, thereby completing the present invention.
第１発明の非水系電解質二次電池用正極材料は、一般式ＬｉｚＮｉ１−ｘ−ｙＣｏｘＭｙＯ２（ただし、０．０１≦ｘ≦０．３５、０≦ｙ≦０．３５、０．９７≦ｚ≦１．２０、Ｍは添加元素であり、Ｍｎ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、ＴｉおよびＡｌから選ばれる少なくとも１種の元素）で表され、一次粒子および一次粒子が凝集して構成された二次粒子からなるリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、の混合物を含むことを特徴とする。
第２発明の非水系電解質二次電池用正極材料は、第１発明において、前記正極材料に含まれるランタンジルコニウム酸リチウム粉末は、粒径が０．０１〜０．５μｍの範囲にあることを特徴とする。
第３発明の非水系電解質二次電池用正極材料は、第１発明または第２発明において、前記正極材料に含まれる、ランタンおよびジルコニウムの合計量が、前記リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％であることを特徴とする。
第４発明の非水系電解質二次電池用正極材料は、第１発明から第３発明のいずれかにおいて、前記ランタンジルコニウム酸リチウムが、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２であることを特徴とする。
第５発明の非水系電解質二次電池用正極材料は、第１発明から第４発明のいずれかにおいて、前記正極材料には、さらに非水系有機溶剤が含まれることを特徴とする。
第６発明の非水系電解質二次電池は、第１発明から第５発明のいずれかの非水系電解質二次電池用正極材料を含む正極を有することを特徴とする。
第７発明の非水系電解質二次電池用正極材料の製造方法は、一般式ＬｉｚＮｉ１−ｘ−ｙＣｏｘＭｙＯ２（ただし、０．０１≦ｘ≦０．３５、０≦ｙ≦０．３５、０．９７≦ｚ≦１．２０、Ｍは添加元素であり、Ｍｎ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、ＴｉおよびＡｌから選ばれる少なくとも１種の元素）で表され、一次粒子および一次粒子が凝集して構成された二次粒子からなるリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、を混合する工程を含むことを特徴とする。
第８発明の非水系電解質二次電池用正極材料の製造方法は、第７発明において、前記ランタンジルコニウム酸リチウム粉末は、粒径が０．０１〜０．５μｍの範囲にあることを特徴とする。
第９発明の非水系電解質二次電池用正極材料の製造方法は、第７発明または第８発明において、前記リチウム金属複合酸化物粉末と、前記ランタンジルコニウム酸リチウムと、を混合する工程の前に、前記リチウム金属複合酸化物粉末を水洗する工程を含むことを特徴とする。
第１０発明の非水系電解質二次電池用正極材料の製造方法は、第７発明から第９発明において、前記正極材料に含まれる、ランタンおよびジルコニウムの合計量が、前記リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％であることを特徴とする。
第１１発明の非水系電解質二次電池用正極材料の製造方法は、第７発明から第１０発明において、前記ランタンジルコニウム酸リチウムが、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２であることを特徴とする。
第１２発明の非水系電解質二次電池用正極材料の製造方法は、第７発明から第１１発明において、前記リチウム金属複合酸化物粉末と、前記ランタンジルコニウム酸リチウムと、を混合する工程において、非水系有機溶剤を添加することを特徴とする。
The positive electrode material for a nonaqueous electrolyte secondary battery of the first invention, the general formula Li z Ni 1-x-y Co x M y O 2 ( however, 0.01 ≦ x ≦ 0.35,0 ≦ y ≦ 0. 35, 0.97 ≦ z ≦ 1.20, M is an additive element and is represented by at least one element selected from Mn, V, Mg, Mo, Nb, Ti and Al), and primary particles and primary particles It contains a mixture of a lithium metal composite oxide powder composed of secondary particles formed by agglomerating and lithium lanthanum zirconate powder.
The positive electrode material for a non-aqueous electrolyte secondary battery of the second invention is the positive electrode material according to the first invention, wherein the lithium lanthanum zirconate powder contained in the positive electrode material has a particle size in the range of 0.01 to 0.5 μm. And
The positive electrode material for a non-aqueous electrolyte secondary battery according to a third aspect of the present invention is the nickel according to the first aspect or the second aspect, wherein the total amount of lanthanum and zirconium contained in the positive electrode material is contained in the lithium metal composite oxide powder. , Cobalt and M with respect to the total number of atoms is 0.1 to 3.0 atomic%.
The positive electrode material for a non-aqueous electrolyte secondary battery according to a fourth aspect of the present invention is characterized in that, in any one of the first to third aspects, the lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 .
The positive electrode material for a non-aqueous electrolyte secondary battery according to a fifth aspect of the present invention is any one of the first to fourth aspects, wherein the positive electrode material further contains a non-aqueous organic solvent.
A non-aqueous electrolyte secondary battery according to a sixth aspect of the invention includes a positive electrode including the positive electrode material for a non-aqueous electrolyte secondary battery according to any of the first to fifth aspects of the invention.
Method for producing a non-aqueous electrolyte secondary battery positive electrode material of the seventh invention, the general formula Li z Ni 1-x-y Co x M y O 2 ( however, 0.01 ≦ x ≦ 0.35,0 ≦ y ≦ 0.35, 0.97 ≦ z ≦ 1.20, where M is an additive element and is represented by at least one element selected from Mn, V, Mg, Mo, Nb, Ti and Al), and primary particles And a step of mixing a lithium metal composite oxide powder composed of secondary particles formed by aggregation of primary particles and a lithium lanthanum zirconate powder.
According to an eighth aspect of the present invention, there is provided a method for producing a positive electrode material for a non-aqueous electrolyte secondary battery. In the seventh aspect, the lithium lanthanum zirconate powder has a particle size in the range of 0.01 to 0.5 μm. .
The method for producing a positive electrode material for a non-aqueous electrolyte secondary battery according to a ninth aspect of the invention is the seventh aspect or the eighth aspect, wherein the lithium metal composite oxide powder and the lithium lanthanum zirconate are mixed before the step. And a step of washing the lithium metal composite oxide powder with water.
According to a tenth aspect of the present invention, there is provided a method for producing a positive electrode material for a non-aqueous electrolyte secondary battery, wherein the total amount of lanthanum and zirconium contained in the positive electrode material is the lithium metal composite oxide powder in the seventh to ninth aspects. It is characterized by 0.1 to 3.0 atomic percent with respect to the total number of nickel, cobalt and M atoms contained.
According to an eleventh aspect of the present invention, there is provided a method for producing a positive electrode material for a non-aqueous electrolyte secondary battery, wherein the lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 in the seventh to tenth aspects.
According to a twelfth aspect of the present invention, there is provided a method for producing a positive electrode material for a nonaqueous electrolyte secondary battery according to the twelfth aspect of the present invention, in the step of mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate. A water-based organic solvent is added.
第１発明によれば、あらかじめ定められたリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、の混合物を含む非水系電解質二次電池用正極材料により、この正極材料が、電池の正極に用いられた場合に、高容量とともに高出力な非水系電解質二次電池を実現することができる。
第２発明によれば、ランタンジルコニウム酸リチウム粉末の粒径が０．０１〜０．５μｍの範囲にあることで、ランタンジルコニウム酸リチウムの正極材料内の分散性を向上させることができ、正極材料内でジルコニウム酸リチウムが均一に混合され、さらに高容量とともに高出力な非水系電解質二次電池を実現することができる。
第３発明によれば、正極材料に含まれる、ランタンとジルコニウムの合計量が、リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％であることにより、非水系電解質二次電池の、高い充放電容量と出力特性を両立することができる。
第４発明によれば、ランタンジルコニウム酸リチウムが、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２であることにより、この化合物が、高いリチウムイオン伝導率を有するものであるので、リチウム金属複合酸化物粉末と混合することで、非水系電解質二次電池の、より高い充放電量と出力特性を得ることができる。
第５発明によれば、正極材料には、さらに非水系有機溶剤が含まれることにより、微粒子であるランタンジルコニウム酸リチウムの凝集が抑制され、正極材料中でのランタンジルコニウム酸リチウムの分散性が一層向上する。
第６発明によれば、非水系電解質二次電池が、第１発明から第５発明のいずれかに記載の非水系電解質二次電池用正極材料を含む正極を有することにより、高容量とともに高出力な非水系電解質二次電池を得ることができる。
第７発明によれば、あらかじめ定められたリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、を混合する、非水系電解質二次電池用正極材料の製造方法により、リチウム金属複合酸化物粉末とランタンジルコニウム酸リチウム粉末との混合物を含む正極材料が得られ、この正極材料が電池の正極に用いられると、高容量とともに高出力な非水系電解質二次電池を実現することができる。
第８発明によれば、粒径が０．０１〜０．５μｍの範囲にあるランタンジルコニウム酸リチウム粉末を用いることで、ランタンジルコニウム酸リチウムの正極材料内の分散性を向上させることができる。
第９発明によれば、リチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、を混合する前に、リチウム金属複合酸化物粉末を水洗する工程を含むことにより、製造された正極材料の電池容量および安全性を向上させることができる。
第１０発明によれば、正極材料に含まれる、ランタンとジルコニウムの合計量が、リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％であることにより、製造された非水系電解質二次電池において、高い充放電容量と出力特性を両立することができる。
第１１発明によれば、前記ランタンジルコニウム酸リチウムが、がＬｉ７Ｌａ３Ｚｒ２Ｏ１２であることにより、この化合物が、高いリチウムイオン伝導率を有するものであるので、これらの化合物がリチウム金属複合酸化物粉末と混合することで、非水系電解質二次電池の高い充放電量と出力特性を得ることができる。
第１２発明によれば、リチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、を混合する際に、非水系有機溶剤を添加することにより、微粒子であるランタンジルコニウム酸リチウムの凝集が抑制され、正極材料中でのランタンジルコニウム酸リチウムの分散性が一層向上する。
According to the first invention, a positive electrode material for a non-aqueous electrolyte secondary battery containing a mixture of a predetermined lithium metal composite oxide powder and a lithium lanthanum zirconate powder is used as the positive electrode of the battery. When used, a non-aqueous electrolyte secondary battery with high capacity and high output can be realized.
According to the second invention, since the particle size of the lithium lanthanum zirconate powder is in the range of 0.01 to 0.5 μm, the dispersibility of the lithium lanthanum zirconate in the positive electrode material can be improved. Thus, a lithium non-aqueous electrolyte secondary battery in which lithium zirconate is uniformly mixed and has high capacity and high output can be realized.
According to the third aspect of the present invention, the total amount of lanthanum and zirconium contained in the positive electrode material is 0.1 to 3.3 with respect to the total number of nickel, cobalt, and M atoms contained in the lithium metal composite oxide powder. By being 0 atomic%, it is possible to achieve both high charge / discharge capacity and output characteristics of the nonaqueous electrolyte secondary battery.
According to the fourth invention, since the lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 , this compound has high lithium ion conductivity, so that it is mixed with the lithium metal composite oxide powder. Thus, higher charge / discharge amount and output characteristics of the non-aqueous electrolyte secondary battery can be obtained.
According to the fifth invention, since the positive electrode material further contains a non-aqueous organic solvent, aggregation of lithium lanthanum zirconate, which is a fine particle, is suppressed, and the dispersibility of lithium lanthanum zirconate in the positive electrode material is further increased. improves.
According to the sixth invention, the non-aqueous electrolyte secondary battery has a positive electrode containing the positive electrode material for a non-aqueous electrolyte secondary battery according to any one of the first to fifth inventions, thereby providing high output with high capacity. A non-aqueous electrolyte secondary battery can be obtained.
According to the seventh invention, a lithium metal composite oxide powder is mixed with a predetermined lithium metal composite oxide powder and a lithium lanthanum zirconate powder, and the method for producing a positive electrode material for a non-aqueous electrolyte secondary battery is used. When a positive electrode material containing a mixture of lithium lanthanum zirconate powder is obtained and this positive electrode material is used for the positive electrode of a battery, a high-capacity and high-power non-aqueous electrolyte secondary battery can be realized.
According to the eighth invention, the dispersibility of the lithium lanthanum zirconate in the positive electrode material can be improved by using the lithium lanthanum zirconate powder having a particle size in the range of 0.01 to 0.5 μm.
According to the ninth aspect of the invention, the battery of the positive electrode material manufactured by including the step of washing the lithium metal composite oxide powder with water before mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate powder. Capacity and safety can be improved.
According to the tenth aspect of the present invention, the total amount of lanthanum and zirconium contained in the positive electrode material is 0.1 to 3.3 with respect to the total number of nickel, cobalt and M atoms contained in the lithium metal composite oxide powder. By being 0 atomic%, the manufactured non-aqueous electrolyte secondary battery can achieve both high charge / discharge capacity and output characteristics.
According to the eleventh invention, since the lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 , this compound has a high lithium ion conductivity. By mixing with the composite oxide powder, a high charge / discharge amount and output characteristics of the non-aqueous electrolyte secondary battery can be obtained.
According to the twelfth invention, when the lithium metal composite oxide powder and the lithium lanthanum zirconate powder are mixed, aggregation of lithium lanthanum zirconate as fine particles is suppressed by adding a non-aqueous organic solvent. The dispersibility of lithium lanthanum zirconate in the positive electrode material is further improved.
以下、本発明について詳細に説明するが、まず本発明に係る正極材料について説明した後、その製造方法および該正極材料を含む正極を有する非水系電解質二次電池について説明する。 Hereinafter, the present invention will be described in detail. First, a positive electrode material according to the present invention will be described, and then a manufacturing method thereof and a nonaqueous electrolyte secondary battery having a positive electrode containing the positive electrode material will be described.
（１）正極材料
本発明の非水系電解質二次電池用正極材料は、一般式ＬｉｚＮｉ１−ｘ−ｙＣｏｘＭｙＯ２（ただし、０．０１≦ｘ≦０．３５、０≦ｙ≦０．３５、０．９７≦ｚ≦１．２０、Ｍは添加元素であり、Ｍｎ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、ＴｉおよびＡｌから選ばれる少なくとも１種の元素）で表され、一次粒子と、一次粒子が凝集して構成された二次粒子からなるリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末と、の混合物を含むことを特徴とするものである。
本発明においては、正極活物質として上記一般式で表されるリチウム金属複合酸化物粉末を用いることにより、高い充放電容量が得られ、さらにリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末を混合することにより、正極材料の充放電容量の低下を抑制しながら出力特性を向上させるものである。
(1) Positive electrode material The positive electrode material for a non-aqueous electrolyte secondary battery of the present invention has a general formula Li z Ni 1-xy Co x M y O 2 (where 0.01 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0.97 ≦ z ≦ 1.20, M is an additive element, and is represented by at least one element selected from Mn, V, Mg, Mo, Nb, Ti, and Al). It includes a mixture of particles, lithium metal composite oxide powder composed of secondary particles formed by aggregation of primary particles, and lithium lanthanum zirconate powder.
In the present invention, a high charge / discharge capacity can be obtained by using the lithium metal composite oxide powder represented by the above general formula as the positive electrode active material. Further, the lithium metal composite oxide powder and the lithium lanthanum zirconate powder By mixing, output characteristics are improved while suppressing a decrease in charge / discharge capacity of the positive electrode material.
通常、正極活物質の表面が異種化合物により完全に被覆されてしまうと、リチウムイオンの移動（インターカレーション）が大きく制限されるため、結果的にリチウム複合酸化物の持つ高容量という長所が損なわれてしまう。また、リチウム複合酸化物中に異種元素を固溶させることは、容量の低下を招きやすい。
一方で、リチウムイオン伝導率が高い化合物はリチウムイオンの移動を促す効果があるため、正極活物質の表面をこのような高リチウム伝導性物質で被覆することにより正極活物質の表面におけるインターカレーションの促進が可能である。しかし、従来の一般的な被覆手法では熱処理等の後処理が必要であり、正極活物質が有する優れた電池特性の劣化を招く恐れもある。
Normally, when the surface of the positive electrode active material is completely covered with a different compound, the movement (intercalation) of lithium ions is greatly limited, resulting in the loss of the high capacity of the lithium composite oxide. It will be. In addition, dissolving different elements in the lithium composite oxide tends to cause a decrease in capacity.
On the other hand, since a compound having high lithium ion conductivity has an effect of promoting the movement of lithium ions, the surface of the positive electrode active material is intercalated on the surface of the positive electrode active material by coating the surface of the positive electrode active material with such a high lithium conductive material. Can be promoted. However, the conventional general coating method requires post-treatment such as heat treatment, which may lead to deterioration of the excellent battery characteristics of the positive electrode active material.
ランタンジルコニウム酸リチウムもリチウムイオン伝導率が高い化合物であるが、ランタンジルコニウム酸リチウムは、リチウム金属複合酸化物と単に混合して、リチウム金属複合酸化物の粒子間に分散させるのみで、リチウムの移動を促進して、大幅に正極抵抗を低減できることを、本発明者は見出した。このランタンジルコニウム酸リチウムが正極材料中に均一に存在し、活物質表面に接触することで、電解液もしくは正極活物質に作用して、電解液と正極活物質界面との間でリチウムの伝導パスが形成され、活物質の反応抵抗を低減することができる。正極抵抗が低減されることで、電池内で損失される電圧が減少し、実際に負荷側に印加される電圧が相対的に高くなるため、高出力を得ることができる。また、負荷側への印加電圧が高くなることで、正極でのリチウムの挿抜が十分に行われるため、電池容量を向上することができる。 Lithium lanthanum zirconate is also a compound with high lithium ion conductivity. However, lithium lanthanum zirconate is simply mixed with the lithium metal composite oxide and dispersed between the particles of the lithium metal composite oxide. The present inventors have found that the positive electrode resistance can be significantly reduced by promoting the above. The lithium lanthanum zirconate is uniformly present in the positive electrode material, and by contacting the active material surface, the lithium lanthanum zirconate acts on the electrolytic solution or the positive electrode active material, and the lithium conduction path between the electrolyte and the positive electrode active material interface And the reaction resistance of the active material can be reduced. By reducing the positive electrode resistance, the voltage lost in the battery is reduced, and the voltage actually applied to the load side becomes relatively high, so that a high output can be obtained. Moreover, since the voltage applied to the load side is increased, lithium is sufficiently inserted and extracted from the positive electrode, so that the battery capacity can be improved.
正極材料内でランタンジルコニウム酸リチウムが不均一に分布された場合は、リチウム金属複合酸化物の粒子間でリチウムイオンの移動が不均一となるため、特定のリチウム金属複合酸化物粒子に負荷がかかり、サイクル特性の悪化や反応抵抗の上昇を招きやすい。したがって、正極材料内において均一にランタンジルコニウム酸リチウムが分布されていることが好ましい。 If lithium lanthanum zirconate is distributed unevenly in the positive electrode material, the movement of lithium ions between the lithium metal composite oxide particles will be non-uniform, which places a load on certain lithium metal composite oxide particles. It tends to cause deterioration of cycle characteristics and increase of reaction resistance. Therefore, it is preferable that lithium lanthanum zirconate is uniformly distributed in the positive electrode material.
したがって、上記ランタンジルコニウム酸リチウムを正極材料内で均一に分散させる必要があり、ランタンジルコニウム酸リチウム粉末の粒径を好ましくは０．０１〜０．５μｍの範囲とすることで、ランタンジルコニウム酸リチウムの分散性をより向上させることができた。その粒径が０．０１μｍ未満では、十分なリチウムイオン伝導度を有しない微細なランタンジルコニウム酸リチウムの粒子が含まれ、このような微粒子が多く存在する部分では上記効果が得られるものの、添加量に応じた効果が得られないことがある。加えて、粉砕コストがかかり過ぎることがある。
また、粒径が０．５μｍを超えると、正極材料内のランタンジルコニウム酸リチウムの分散の均一性が低下するため、上記効果が得られるものの、添加量に応じた効果が得られないことがある。粒径は、レーザー回折散乱法を用いて測定することができ、Ｄ１０以上Ｄ９０以下を粒径の範囲とする。ここで、Ｄ１０は、各粒径における粒子数を粒径の小さい側から累積し、その累積体積が全粒子の合計体積の１０％となる粒径を意味している。また、Ｄ９０は、同様に粒子数を累積し、その累積体積が全粒子の合計体積の９０％となる粒径を意味している。
なお、粒径が上記範囲を超える場合には、混合前に粉砕することが好ましい。
Therefore, the lithium lanthanum zirconate needs to be uniformly dispersed in the positive electrode material, and the particle size of the lithium lanthanum zirconate powder is preferably in the range of 0.01 to 0.5 μm. Dispersibility could be further improved. When the particle size is less than 0.01 μm, fine lithium lanthanum zirconate particles that do not have sufficient lithium ion conductivity are included, and the above effect is obtained in a portion where such fine particles are present, but the added amount Depending on the situation, the effect may not be obtained. In addition, the grinding cost may be too high.
Further, if the particle size exceeds 0.5 μm, the uniformity of the dispersion of lithium lanthanum zirconate in the positive electrode material is lowered, so the above effect can be obtained, but the effect according to the addition amount may not be obtained. . The particle size can be measured using a laser diffraction scattering method, and D10 or more and D90 or less are set as the particle size range. Here, D10 means a particle size in which the number of particles in each particle size is accumulated from the smaller particle size side and the accumulated volume becomes 10% of the total volume of all particles. Similarly, D90 means a particle size in which the number of particles is accumulated and the accumulated volume is 90% of the total volume of all particles.
In addition, when a particle size exceeds the said range, it is preferable to grind | pulverize before mixing.
この正極材料に含まれるランタンとジルコニウムの合計量は、混合するリチウム金属複合酸化物に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％とすることが好ましい。これにより、高い充放電容量と出力特性を両立することができる。ランタンとジルコニウム量の合計が０．１原子％未満では、出力特性の改善効果が十分に得られない場合があり、ランタンとジルコニウム量の合計が３．０原子％を超えると、ランタンジルコニウム酸リチウムが多くなり過ぎてリチウム金属複合酸化物と電解液のリチウム伝導が阻害され、充放電容量が、特に正極材料の重量あたりの充放電容量が低下することがある。 The total amount of lanthanum and zirconium contained in this positive electrode material is 0.1 to 3.0 atomic% with respect to the total number of nickel, cobalt, and M atoms contained in the mixed lithium metal composite oxide. Is preferred. Thereby, it is possible to achieve both high charge / discharge capacity and output characteristics. When the total amount of lanthanum and zirconium is less than 0.1 atomic%, the effect of improving the output characteristics may not be sufficiently obtained. When the total amount of lanthanum and zirconium exceeds 3.0 atomic%, lithium lanthanum zirconate As a result, the lithium conductivity of the lithium metal composite oxide and the electrolytic solution is hindered, and the charge / discharge capacity, particularly the charge / discharge capacity per weight of the positive electrode material, may decrease.
このランタンジルコニウム酸リチウムがＬｉ７Ｌａ３Ｚｒ２Ｏ１２であることが好ましい。 このランタンジルコニウム酸リチウムは、高いリチウムイオン伝導率を有するものであり、リチウム金属複合酸化物粉末と混合することで上記効果が十分に得られる。 The lithium lanthanum zirconate is preferably Li 7 La 3 Zr 2 O 12 . This lithium lanthanum zirconate has a high lithium ion conductivity, and the above effect can be sufficiently obtained by mixing with lithium metal composite oxide powder.
さらに、正極材料は、非水系有機溶剤をさらに含むことが好ましい。これにより、微粒子であるランタンジルコニウム酸リチウムの凝集が抑制され、正極材料中でのランタンジルコニウム酸リチウムの分散性が一層向上する。非水系有機溶剤としては、例えばＮ−メチル−２−ピロリジノンが該当するが、特にこれに限定されない。しかし、後述する正極の作成時に使用する非水系有機溶剤と同じものを用いるのが望ましい。使用する非水系有機溶剤を限定することで、異物混入の可能性を抑えることができるからである。 Furthermore, the positive electrode material preferably further contains a non-aqueous organic solvent. Thereby, aggregation of lithium lanthanum zirconate as fine particles is suppressed, and dispersibility of lithium lanthanum zirconate in the positive electrode material is further improved. Examples of the non-aqueous organic solvent include N-methyl-2-pyrrolidinone, but are not particularly limited thereto. However, it is desirable to use the same non-aqueous organic solvent that is used when producing the positive electrode described later. This is because by limiting the non-aqueous organic solvent to be used, the possibility of foreign matter contamination can be suppressed.
リチウム金属複合酸化物のリチウム量は、リチウム金属複合酸化物中のニッケル、コバルトおよびＭの原子数の和（Ｍｅ）とリチウム（Ｌｉ）の原子数との比（Ｌｉ／Ｍｅ）で０．９７〜１．２０である。
Ｌｉ／Ｍｅが０．９７未満であると、上記正極材量を用いた非水系電解質二次電池における正極の反応抵抗が大きくなるため、電池の出力が低くなってしまう。また、Ｌｉ／Ｍｅが１．２０を超えると、正極活材料の放電容量が低下するとともに、正極の反応抵抗も増加してしまう。そこで、より大きな放電容量を得るためには、Ｌｉ／Ｍｅを１．１０以下とすることが好ましい。
The lithium amount of the lithium metal composite oxide is 0.97 in terms of the ratio (Li / Me) of the sum of the number of atoms of nickel, cobalt, and M (Me) in the lithium metal composite oxide to the number of atoms of lithium (Li). ~ 1.20.
When Li / Me is less than 0.97, the reaction resistance of the positive electrode in the non-aqueous electrolyte secondary battery using the above positive electrode material amount increases, and the output of the battery becomes low. On the other hand, when Li / Me exceeds 1.20, the discharge capacity of the positive electrode active material decreases and the reaction resistance of the positive electrode also increases. Therefore, in order to obtain a larger discharge capacity, Li / Me is preferably set to 1.10 or less.
Ｃｏおよび添加元素Ｍは、サイクル特性や出力特性などの電池特性を向上させるために添加するものであるが、これらの添加量を示すｘおよびｙが０．３５を超えると、Ｒｅｄｏｘ反応に貢献するＮｉが減少するため、電池容量が低下する。
一方、Ｃｏの添加量を示すｘが０．０１未満になると、サイクル特性や熱安定性が十分に得られない。したがって、電池に用いたときに十分な電池容量を得るためには、Ｍの添加量を示すｙを０．１５以下とすることが好ましい。
Co and additive element M are added in order to improve battery characteristics such as cycle characteristics and output characteristics. If x and y indicating these addition amounts exceed 0.35, they contribute to the Redox reaction. Since Ni decreases, the battery capacity decreases.
On the other hand, when x indicating the amount of Co added is less than 0.01, cycle characteristics and thermal stability cannot be obtained sufficiently. Therefore, in order to obtain a sufficient battery capacity when used in a battery, it is preferable that y indicating the amount of addition of M is 0.15 or less.
また、電解液との接触面積を多くすることが、出力特性の向上に有利であることから、一次粒子および一次粒子が凝集して構成された二次粒子からなるリチウム金属複合酸化物粒子を用いる。
リチウム金属複合酸化物粉末は、比表面積が０．５〜２ｍ２／ｇであることが好ましい。比表面積が０．５ｍ２／ｇ未満になると、電解液との接触が十分に得られず、出力特性や電池容量が低下することがある。また、比表面積が２ｍ２／ｇを超えると、電解液の分解が促進され熱安定性が低下するがある。比表面積を０．５〜２ｍ２／ｇとすることにより、電解液との接触を高めて出力特性や電池容量をより良好なものとするとともに熱安定性安も確保することができる。また、正極材料の好ましい態様においては、正極材料の比表面積はリチウム金属複合酸化物粉末と同程度となる。
In addition, since it is advantageous for improving the output characteristics to increase the contact area with the electrolytic solution, lithium metal composite oxide particles composed of primary particles and secondary particles formed by aggregation of the primary particles are used. .
The lithium metal composite oxide powder preferably has a specific surface area of 0.5 to 2 m 2 / g. When the specific surface area is less than 0.5 m 2 / g, sufficient contact with the electrolytic solution may not be obtained, and output characteristics and battery capacity may be reduced. On the other hand, if the specific surface area exceeds 2 m 2 / g, the decomposition of the electrolyte solution is promoted and the thermal stability is lowered. By setting the specific surface area to 0.5 to 2 m 2 / g, it is possible to enhance contact with the electrolytic solution to improve output characteristics and battery capacity and to ensure low thermal stability. Moreover, in the preferable aspect of positive electrode material, the specific surface area of positive electrode material becomes comparable as lithium metal complex oxide powder.
本発明の正極材料は、リチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウムの微粉末を混合することにより出力特性を改善したものであり、正極活物質としてのリチウム金属複合酸化物の粒径、タップ密度などの粉体特性は、通常に用いられる正極活物質の範囲内であれば良く、また、リチウム金属複合酸化物は、公知の方法で得られたものでよく、上記組成および粉体特性を満たすものを用いることができる。
リチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末を混合することにより得られる効果は、たとえば、リチウムコバルト系複合酸化物、リチウムマンガン系複合酸化物、リチウムニッケルコバルトマンガン系複合酸化物など、本発明で掲げた正極活物質だけでなく一般的に使用されるリチウム二次電池用正極活物質にも適用できる。
The positive electrode material of the present invention has improved output characteristics by mixing a lithium metal composite oxide powder and a fine powder of lithium lanthanum zirconate, the particle size of the lithium metal composite oxide as the positive electrode active material, The powder properties such as tap density may be within the range of the normally used positive electrode active material, and the lithium metal composite oxide may be obtained by a known method. What satisfies the condition can be used.
The effect obtained by mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate powder is, for example, such as lithium cobalt composite oxide, lithium manganese composite oxide, lithium nickel cobalt manganese composite oxide, etc. The present invention can be applied not only to the positive electrode active material described in the invention, but also to a commonly used positive electrode active material for a lithium secondary battery.
図１には本発明の実施形態に係る非水系電解質二次電池用正極材料の製造方法を示す。本発明の非水系電解質二次電池用正極材料の製造方法は、母材としての正極活物質として一般式ＬｉｚＮｉ１−ｘ−ｙＣｏｘＭｙＯ２（ただし、０．０１≦ｘ≦０．３５、０≦ｙ≦０．３５、０．９７≦ｚ≦１．２０、Ｍは、Ｍｎ、Ｖ、Ｍｇ、Ｍｏ、Ｎｂ、ＴｉおよびＡｌから選ばれる少なくとも１種の元素）で表され、一次粒子および一次粒子が凝集して構成された二次粒子からなるリチウム金属複合酸化物粉末と、ランタンジルコニウム酸リチウム粉末、好ましくは粒径０．０１〜０．５μｍのランタンジルコニウム酸リチウム粉末を混合するものである。 FIG. 1 shows a method for producing a positive electrode material for a non-aqueous electrolyte secondary battery according to an embodiment of the present invention. Method for producing a cathode material for a nonaqueous electrolyte secondary battery of the present invention have the general formula as a cathode active material for a base material Li z Ni 1-x-y Co x M y O 2 ( however, 0.01 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.35, 0.97 ≦ z ≦ 1.20, M is represented by at least one element selected from Mn, V, Mg, Mo, Nb, Ti and Al) A lithium metal composite oxide powder composed of primary particles and secondary particles formed by agglomeration of primary particles, lithium lanthanum zirconate powder, preferably 0.01 to 0.5 μm of lanthanum zirconate powder To be mixed.
リチウム金属複合酸化物粉末とランタンジルコニウム酸リチウム粉末は、正極材料内で微粒子を均一に分散させ、正極活物質表面に微粒子を接触させるため十分混合する。 The lithium metal composite oxide powder and the lithium lanthanum zirconate powder are mixed sufficiently to disperse the fine particles uniformly in the positive electrode material and bring the fine particles into contact with the surface of the positive electrode active material.
さらに、前記リチウム金属複合酸化物粉末と、前記ランタンジルコニウム酸リチウム粉末を混合する際に、非水系有機溶剤を添加することが好ましい。これにより、ランタンジルコニウム酸リチウムの凝集が抑制され、正極材料内で微粒子をさらに均一に分散させることができる。非水系有機溶剤としては、例えばＮ−メチル−２−ピロリジノンが該当するが、特にこれに限定されない。しかし、後述する正極の作成時に使用する非水系有機溶剤と同じものを用いるのが望ましい。使用する非水系有機溶剤を限定することで、異物混入の可能性を抑えることができるからである。 Furthermore, it is preferable to add a non-aqueous organic solvent when mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate powder. Thereby, aggregation of lithium lanthanum zirconate is suppressed, and fine particles can be more uniformly dispersed in the positive electrode material. Examples of the non-aqueous organic solvent include N-methyl-2-pyrrolidinone, but are not particularly limited thereto. However, it is desirable to use the same non-aqueous organic solvent that is used when producing the positive electrode described later. This is because by limiting the non-aqueous organic solvent to be used, the possibility of foreign matter contamination can be suppressed.
その混合には、一般的な混合機を使用することができ、例えば、シェーカーミキサーやレーディゲミキサー、ジュリアミキサー、Ｖブレンダーなどを用いてリチウム金属複合酸化物粒子の形骸が破壊されない程度で、ランタンジルコニウム酸リチウムを十分に混合してやればよい。
これにより、ランタンジルコニウム酸リチウムの微粒子を、リチウム金属複合酸化物粉末表面に均一に分布させることができる。
For the mixing, a general mixer can be used. For example, the shape of the lithium metal composite oxide particles is not destroyed using a shaker mixer, a Laedige mixer, a Julia mixer, a V blender, etc. What is necessary is just to fully mix lithium lanthanum zirconate.
Thereby, the fine particles of lithium lanthanum zirconate can be uniformly distributed on the surface of the lithium metal composite oxide powder.
本発明の製造方法においては、正極材料の電池容量および熱安定性を向上させるために、上記混合工程の前に、さらにリチウム金属複合酸化物粉末を水洗することができる。
この水洗は、公知の方法および条件でよく、リチウム金属複合酸化物粉末から過度にリチウムが溶出して電池特性が劣化しない範囲で行えばよい。
水洗した場合には、ランタンジルコニウム酸リチウム粉末と混合しても、固液分離のみで乾燥せずにランタンジルコニウム酸リチウム粉末と混合した後、乾燥してもいずれの方法でもよい。
また乾燥は、公知の方法および条件でよく、リチウム金属複合酸化物の電池特性が劣化しない範囲で行えばよい。
In the production method of the present invention, in order to improve the battery capacity and thermal stability of the positive electrode material, the lithium metal composite oxide powder can be further washed with water before the mixing step.
This washing with water may be performed by a known method and conditions as long as lithium is not excessively eluted from the lithium metal composite oxide powder and the battery characteristics are not deteriorated.
When washed with water, it may be mixed with the lithium lanthanum zirconate powder, or may be mixed with the lithium lanthanum zirconate powder without being dried only by solid-liquid separation and then dried.
The drying may be performed by a known method and conditions as long as the battery characteristics of the lithium metal composite oxide are not deteriorated.
（２）非水系電解質二次電池
本発明の非水系電解質二次電池は、正極、負極および非水系電解液などからなり、一般の非水系電解質二次電池と同様の構成要素により構成される。
なお、以下で説明する実施形態は例示に過ぎず、本発明の非水系電解質二次電池は、本明細書に記載されている実施形態を基に、当業者の知識に基づいて種々の変更、改良を施した形態で実施することができる。また、本発明の非水系電解質二次電池は、その用途を特に限定するものではない。
(2) Non-aqueous electrolyte secondary battery The non-aqueous electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode, a non-aqueous electrolyte solution, and the like, and includes the same components as those of a general non-aqueous electrolyte secondary battery.
The embodiment described below is merely an example, and the nonaqueous electrolyte secondary battery of the present invention can be variously modified based on the knowledge of those skilled in the art based on the embodiment described in the present specification. It can be implemented in an improved form. Moreover, the use of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited.
（ａ）正極
本発明による非水系電解質二次電池用正極材料を用いて、例えば、以下のようにして、非水系電解質二次電池の正極を作製する。
まず、粉末状の正極材料、導電材、結着剤を混合し、さらに必要に応じて活性炭、粘度調整等の目的の溶剤を添加し、これを混練して正極合材ペーストを作製する。
ここで、正極合材ペースト中のそれぞれの混合比も、非水系電解質二次電池の性能を決定する重要な要素となる。
そのため、溶剤を除いた正極合材の固形分の全質量を１００質量部とした場合、一般の非水系電解質二次電池の正極と同様、正極活物質の含有量を６０〜９５質量部とし、導電材の含有量を１〜２０質量部とし、結着剤の含有量を１〜２０質量部とすることが望ましい。
(A) Positive electrode Using the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention, for example, a positive electrode of a non-aqueous electrolyte secondary battery is produced as follows.
First, a powdered positive electrode material, a conductive material, and a binder are mixed, and if necessary, a target solvent such as activated carbon and viscosity adjustment is added and kneaded to prepare a positive electrode mixture paste.
Here, each mixing ratio in the positive electrode mixture paste is also an important factor that determines the performance of the non-aqueous electrolyte secondary battery.
Therefore, when the total mass of the solid content of the positive electrode mixture excluding the solvent is 100 parts by mass, the content of the positive electrode active material is 60 to 95 parts by mass, like the positive electrode of a general nonaqueous electrolyte secondary battery, It is desirable that the content of the conductive material is 1 to 20 parts by mass and the content of the binder is 1 to 20 parts by mass.
得られた正極合材ペーストを、例えば、アルミニウム箔製の集電体の表面に塗布し、乾燥して、溶剤を飛散させる。必要に応じ、電極密度を高めるべく、ロールプレス等により加圧することもある。
このようにして、シート状の正極を作製することができる。
作製したシート状の正極は、目的とする電池に応じて適当な大きさに裁断等をして、電池の作製に供することができる。ただし、正極の作製方法は、前記例示のものに限られることなく、他の方法によってもよい。
The obtained positive electrode mixture paste is applied to the surface of a current collector made of, for example, an aluminum foil and dried to disperse the solvent. If necessary, pressurization may be performed by a roll press or the like to increase the electrode density.
In this way, a sheet-like positive electrode can be produced.
The produced sheet-like positive electrode can be cut into an appropriate size or the like according to the intended battery and used for battery production. However, the method for manufacturing the positive electrode is not limited to the above-described examples, and other methods may be used.
正極の作製にあたって、導電剤としては、例えば、黒鉛（天然黒鉛、人造黒鉛、膨張黒鉛など）や、アセチレンブラック、ケッチェンブラックなどのカーボンブラック系材料などを用いることができる。
結着剤は、活物質粒子をつなぎ止める役割を果たすもので、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、フッ素ゴム、エチレンプロピレンジエンゴム、スチレンブタジエン、セルロース系樹脂、ポリアクリル酸などを用いることができる。
必要に応じ、正極活物質、導電材、活性炭を分散させ、結着剤を溶解する溶剤を正極合材に添加する。
使用する溶剤としては、具体的には、Ｎ−メチル−２−ピロリドン等の有機溶剤を用いることができる。また、正極合材には、電気二重層容量を増加させるために、活性炭を添加することができる。
In producing the positive electrode, as the conductive agent, for example, graphite (natural graphite, artificial graphite, expanded graphite, etc.), carbon black materials such as acetylene black, ketjen black, and the like can be used.
The binder plays a role of anchoring the active material particles. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene rubber, styrene butadiene, cellulose resin, polyacrylic, and the like. An acid or the like can be used.
If necessary, a positive electrode active material, a conductive material, and activated carbon are dispersed, and a solvent that dissolves the binder is added to the positive electrode mixture.
Specifically, an organic solvent such as N-methyl-2-pyrrolidone can be used as the solvent to be used. Activated carbon can be added to the positive electrode mixture in order to increase the electric double layer capacity.
（ｂ）負極
負極には、金属リチウムやリチウム合金等、あるいは、リチウムイオンを吸蔵および脱離できる負極活物質に、結着剤を混合し、適当な溶剤を加えてペースト状にした負極合材を、銅等の金属箔集電体の表面に塗布し、乾燥し、必要に応じて電極密度を高めるべく圧縮して形成したものを使用する。
(B) Negative electrode A negative electrode mixture in which a negative electrode active material capable of occluding and desorbing lithium ions is mixed with a binder and an appropriate solvent is added to the negative electrode. Is applied to the surface of a metal foil current collector such as copper, dried, and compressed to increase the electrode density as necessary.
負極活物質としては、例えば、天然黒鉛、人造黒鉛、フェノール樹脂等の有機化合物焼成体、コークス等の炭素物質の粉状体を用いることができる。
この場合、負極結着剤としては、正極同様、ＰＶＤＦ等の含フッ素樹脂等を用いることができ、これらの活物質および結着剤を分散させる溶剤としては、Ｎ−メチル−２−ピロリドン等の有機溶剤を用いることができる。
As the negative electrode active material, for example, natural graphite, artificial graphite, a fired organic compound such as phenol resin, or a powdery carbon material such as coke can be used.
In this case, as the negative electrode binder, a fluorine-containing resin such as PVDF can be used as in the case of the positive electrode, and as a solvent for dispersing these active materials and the binder, N-methyl-2-pyrrolidone or the like can be used. Organic solvents can be used.
（ｃ）セパレータ
正極と負極との間には、セパレータを挟み込んで配置する。
セパレータは、正極と負極とを分離し、電解質を保持するものであり、ポリエチレン、ポリプロピレン等の薄い膜で、微少な孔を多数有する膜を用いることができる。
(C) Separator A separator is interposed between the positive electrode and the negative electrode.
The separator separates the positive electrode and the negative electrode and retains the electrolyte, and a thin film such as polyethylene or polypropylene and a film having many minute holes can be used.
（ｄ）非水系電解液
非水系電解液は、支持塩としてのリチウム塩を有機溶媒に溶解したものである。
有機溶媒としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、トリフルオロプロピレンカーボネート等の環状カーボネート、また、ジエチルカーボネート、ジメチルカーボネート、エチルメチルカーボネート、ジプロピルカーボネート等の鎖状カーボネート、さらに、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジメトキシエタン等のエーテル化合物、エチルメチルスルホン、ブタンスルトン等の硫黄化合物、リン酸トリエチル、リン酸トリオクチル等のリン化合物等から選ばれる１種を単独で、あるいは２種以上を混合して用いることができる。
(D) Non-aqueous electrolyte The non-aqueous electrolyte is obtained by dissolving a lithium salt as a supporting salt in an organic solvent.
Examples of the organic solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and trifluoropropylene carbonate; chain carbonates such as diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate; and tetrahydrofuran, 2- One kind selected from ether compounds such as methyltetrahydrofuran and dimethoxyethane, sulfur compounds such as ethylmethylsulfone and butanesultone, phosphorus compounds such as triethyl phosphate and trioctyl phosphate, etc. are used alone or in admixture of two or more. be able to.
支持塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＡｓＦ６、ＬｉＮ（ＣＦ３ＳＯ２）２等、およびそれらの複合塩を用いることができる。
さらに、非水系電解液は、ラジカル捕捉剤、界面活性剤および難燃剤等を含んでいてもよい。
As the supporting salt, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , or a composite salt thereof can be used.
Furthermore, the non-aqueous electrolyte solution may contain a radical scavenger, a surfactant, a flame retardant, and the like.
（ｅ）非水系電解質二次電池の形状、構成
以上のように説明してきた正極、負極、セパレータおよび非水系電解液で構成される本発明の非水系電解質二次電池の形状は、円筒型、積層型等、種々のものとすることができる。
いずれの形状を採る場合であっても、正極および負極を、セパレータを介して積層させて電極体とし、得られた電極体に、非水系電解液を含浸させ、正極集電体と外部に通ずる正極端子との間、および、負極集電体と外部に通ずる負極端子との間を、集電用リード等を用いて接続し、電池ケースに密閉して、非水系電解質二次電池を完成させる。
(E) Shape and configuration of non-aqueous electrolyte secondary battery The shape of the non-aqueous electrolyte secondary battery of the present invention composed of the positive electrode, the negative electrode, the separator, and the non-aqueous electrolyte described above is cylindrical, Various types such as a laminated type can be used.
In any case, the positive electrode and the negative electrode are laminated via a separator to form an electrode body, and the obtained electrode body is impregnated with a non-aqueous electrolyte and communicated with the positive electrode current collector and the outside. The positive electrode terminal and the negative electrode current collector and the negative electrode terminal communicating with the outside are connected using a current collecting lead or the like and sealed in a battery case to complete a non-aqueous electrolyte secondary battery. .
（ｆ）特性
本発明の正極材料を含む正極を有する非水系電解質二次電池は、高容量で高出力となる。
特により好ましい形態で得られた正極材料を用いた非水系電解質二次電池は、例えば、２０３２型コイン電池の正極に用いた場合、１６５ｍＡｈ／ｇ以上の高い初期放電容量と低い正極抵抗が得られ、さらに高容量で高出力である。また、熱安定性が高く、安全性においても優れているものである。
(F) Characteristics A nonaqueous electrolyte secondary battery having a positive electrode containing the positive electrode material of the present invention has a high capacity and a high output.
A non-aqueous electrolyte secondary battery using a positive electrode material obtained in a more preferable form can obtain a high initial discharge capacity of 165 mAh / g or more and a low positive electrode resistance when used for the positive electrode of a 2032 type coin battery, for example. Higher capacity and higher output. Further, it has high thermal stability and is excellent in safety.
正極界面抵抗はコイン型セルを充電電位４．０Ｖまで充電して、周波数応答アナライザおよびポテンショガルバノスタットを使用して、交流インピーダンス測定を行い図２に模式図として示すようなインピーダンススペクトルを得た。得られたインピーダンススペクトルには、高周波領域と中間周波領域とに２つの半円が観測され、低周波領域に直線が観察されていることから、図３に示す等価回路モデルを組んで正極界面抵抗を解析した。ここで、Ｒｓはバルク抵抗、Ｒ１は正極被膜抵抗、Ｒｃｔは電解液／正極界面抵抗（界面のＬｉ＋移動抵抗）、Ｗはワーブルグ成分を示す。 For the positive electrode interface resistance, a coin-type cell was charged to a charging potential of 4.0 V, an AC impedance measurement was performed using a frequency response analyzer and a potentio galvanostat, and an impedance spectrum as shown in a schematic diagram in FIG. 2 was obtained. In the obtained impedance spectrum, two semicircles are observed in the high frequency region and the intermediate frequency region, and a straight line is observed in the low frequency region. Therefore, an equivalent circuit model shown in FIG. Was analyzed. Here, Rs is a bulk resistance, R1 is a positive electrode film resistance, Rct is an electrolyte / positive electrode interface resistance (Li + movement resistance at the interface), and W is a Warburg component.
本発明により得られた正極材料を用いた正極を有する非水系電解質二次電池について、その正極界面抵抗を確認した。
以下、本発明の実施例を用いて具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。
The positive electrode interface resistance was confirmed about the non-aqueous electrolyte secondary battery which has a positive electrode using the positive electrode material obtained by this invention.
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
（電池の製造および評価）
得られた非水系電解質二次電池用正極材料の評価は、以下のように図４に示す電池を作製し、正極界面抵抗を測定することで行なった。
非水系電解質二次電池用正極材料５２．５ｍｇ、アセチレンブラック１５ｍｇ、およびポリテトラフッ化エチレン樹脂（ＰＴＦＥ）７．５ｍｇを混合し、１００ＭＰａの圧力で直径１１ｍｍ、厚み１００μｍにプレス成形して、正極（評価用電極）１を作製した。
次に作製した正極１を真空乾燥機中１２０℃で１２時間乾燥した。
乾燥した正極（評価用電極）１、負極２、セパレータ３および電解液とを用いて、図３のコイン型電池１０を、露点が−８０℃に管理されたＡｒ雰囲気のグローブボックス内で作製した。
負極２には、直径１４ｍｍの円盤状に打ち抜かれた平均粒径２０μｍ程度の黒鉛粉末とポリフッ化ビニリデンが銅箔に塗布された負極シートを用い、電解液には、１ＭのＬｉＰＦ６を支持電解質とするエチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）の等量混合液（宇部興産株式会社製）を用いた。セパレータ３には膜厚２５μｍのポリエチレン多孔膜を用いた。また、コイン型電池１０は、ガスケット４とウェーブワッシャー５を有し、正極缶６と負極缶７とでコイン状の電池に組み立てられた。
(Battery manufacture and evaluation)
The obtained positive electrode material for a non-aqueous electrolyte secondary battery was evaluated by preparing the battery shown in FIG. 4 as follows and measuring the positive electrode interface resistance.
52.5 mg of a positive electrode material for a non-aqueous electrolyte secondary battery, 15 mg of acetylene black, and 7.5 mg of polytetrafluoroethylene resin (PTFE) are mixed, press molded to a diameter of 11 mm and a thickness of 100 μm at a pressure of 100 MPa, and a positive electrode (evaluation Electrode) 1 was produced.
Next, the produced positive electrode 1 was dried at 120 ° C. for 12 hours in a vacuum dryer.
Using the dried positive electrode (evaluation electrode) 1, negative electrode 2, separator 3, and electrolyte solution, the coin-type battery 10 of FIG. 3 was produced in a glove box in an Ar atmosphere in which the dew point was controlled at −80 ° C. .
For the negative electrode 2, a negative electrode sheet in which a graphite powder punched into a disk shape with a diameter of 14 mm and an average particle diameter of about 20 μm and polyvinylidene fluoride are applied to a copper foil is used, and 1 M LiPF 6 is used as the electrolyte for the electrolyte. An equivalent mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC) (manufactured by Ube Industries, Ltd.) was used. As the separator 3, a polyethylene porous film having a film thickness of 25 μm was used. The coin-type battery 10 includes a gasket 4 and a wave washer 5, and the positive electrode can 6 and the negative electrode can 7 are assembled into a coin-shaped battery.
製造したコイン型電池１０の性能を示す正極抵抗は、コイン型電池１０を充電電位４．０Ｖで充電して、周波数応答アナライザおよびポテンショガルバノスタット（ソーラトロン社製、１２５５Ｂ）を使用して交流インピーダンス法により測定して図２に示すインピーダンススペクトルを得た。
得られたインピーダンススペクトルには、高周波領域と中間周波領域とに２つの半円が観測され、低周波領域に直線が観察されていることから、図３に示す等価回路モデルを組んで正極界面抵抗を解析した。ここで、Ｒｓはバルク抵抗、Ｒ１は正極被膜抵抗、Ｒｃｔは電解液/正極界面抵抗（界面のLi+移動抵抗）、Ｗはワーブルグ成分、ＣＰＥ１、ＣＰＥ２は定相要素を示す。
The positive electrode resistance indicating the performance of the manufactured coin-type battery 10 is obtained by charging the coin-type battery 10 at a charging potential of 4.0 V, and using an AC impedance method using a frequency response analyzer and potentiogalvanostat (1255B manufactured by Solartron). The impedance spectrum shown in FIG.
In the obtained impedance spectrum, two semicircles are observed in the high frequency region and the intermediate frequency region, and a straight line is observed in the low frequency region. Therefore, an equivalent circuit model shown in FIG. Was analyzed. Here, Rs is bulk resistance, R1 is positive electrode film resistance, Rct is electrolyte / positive electrode interface resistance (Li + movement resistance at the interface), W is a Warburg component, and CPE1 and CPE2 are constant phase elements.
（実施例１）
ニッケルを主成分とする酸化物と水酸化リチウムを混合して焼成する公知の技術で得られたＬｉ１．０２Ｎｉ０．８２Ｃｏ０．１５Ａｌ０．０３Ｏ２で表されるリチウム金属複合酸化物粉末を１．５ｇ／ｍｌの条件で水洗して正極材料の母材とした。母材の比表面積は、１．３５ｍ２／ｇであった。
なお、組成はＩＣＰ法により分析しランタンジルコニウム酸リチウム粉末の粒径はレーザー回折散乱法により確認を行い、比表面積は窒素ガス吸着ＢＥＴ法を用いて評価した。
(Example 1)
A lithium metal composite represented by Li 1.02 Ni 0.82 Co 0.15 Al 0.03 O 2 obtained by a known technique in which an oxide mainly composed of nickel and lithium hydroxide are mixed and fired The oxide powder was washed with water under the condition of 1.5 g / ml to obtain a base material for the positive electrode material. The specific surface area of the base material was 1.35 m 2 / g.
The composition was analyzed by the ICP method, the particle size of the lithium lanthanum zirconate powder was confirmed by the laser diffraction scattering method, and the specific surface area was evaluated by using the nitrogen gas adsorption BET method.
ＬａＺｒ添加材料である粒径５〜８０μｍのランタンジルコニウム酸リチウム（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２）粉末を、自転・公転ミキサーを用いて十分に粉砕し、粒径０．０１〜０．５μｍのジルコニウム酸リチウム粉末を得た。作製したリチウム金属複合酸化物粉末２０ｇに、粒径０．０１〜０．５μｍのランタンジルコニウム酸リチウム（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２）粉末０．１８ｇを添加し、さらに、Ｎ−メチル−２−ピロリドンを加えて、自転・公転ミキサーを用いて十分に混合して、ランタンジルコニウム酸リチウム粉末とリチウム金属複合酸化物粉末の混合物を得て正極材料とした。
この正極材料中のＬａとＺｒの含有量をＩＣＰ法により分析したところ、ニッケル、コバルトおよびＭの原子数の合計に対して０．１原子％の組成であることを確認した。
これより、ランタンジルコニウム酸リチウム粉末とリチウム金属複合酸化物粉末の混合物の配合と正極材料の組成が同等であることも確認した。
A LaZr-added lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 12 ) powder having a particle size of 5 to 80 μm is sufficiently pulverized using a rotating / revolving mixer, and a particle size of 0.01 to 0.5 μm is obtained. A lithium zirconate powder was obtained. To 20 g of the prepared lithium metal composite oxide powder, 0.18 g of lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 12 ) powder having a particle size of 0.01 to 0.5 μm was added, and further N-methyl-2 -Pyrrolidone was added and mixed thoroughly using a rotation / revolution mixer to obtain a mixture of lithium lanthanum zirconate powder and lithium metal composite oxide powder to be a positive electrode material.
When the contents of La and Zr in this positive electrode material were analyzed by the ICP method, it was confirmed that the composition was 0.1 atomic% with respect to the total number of nickel, cobalt and M atoms.
From this, it was also confirmed that the mixture of the mixture of lithium lanthanum zirconate powder and lithium metal composite oxide powder and the composition of the positive electrode material were equivalent.
（電池評価）
得られた正極材料を用いて形成された正極を有するコイン型電池１０について、電池特性を評価した。
(Battery evaluation)
Battery characteristics of the coin-type battery 10 having a positive electrode formed using the obtained positive electrode material were evaluated.
（実施例２）
母材となるリチウム金属複合酸化物粉末にランタンジルコニウム酸リチウム（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２）粉末０．５５ｇを添加した以外は、実施例１と同様にして作製した非水系電解質二次電池用正極材料を用いてコイン型電池を作製し、その電池評価を行った。この時のＬａとＺｒの含有率の和は０．３原子％であった。
(Example 2)
A non-aqueous electrolyte secondary battery produced in the same manner as in Example 1 except that 0.55 g of lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 12 ) powder was added to the lithium metal composite oxide powder as the base material. A coin-type battery was fabricated using the positive electrode material for the battery, and the battery was evaluated. At this time, the sum of the contents of La and Zr was 0.3 atomic%.
（実施例３）
母材となるリチウム金属複合酸化物粉末にランタンジルコニウム酸リチウム（Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２）粉末０．９２ｇを添加した以外は、実施例１と同様にして作製した非水系電解質二次電池用正極材料を用いてコイン型電池を作製し、その電池評価を行った。この時のＬａとＺｒの含有率の和は０．５原子％であった。
(Example 3)
A non-aqueous electrolyte secondary battery produced in the same manner as in Example 1 except that 0.92 g of lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 12 ) powder was added to the lithium metal composite oxide powder as the base material. A coin-type battery was fabricated using the positive electrode material for the battery, and the battery was evaluated. At this time, the sum of the contents of La and Zr was 0.5 atomic%.
（比較例１）
実施例１で母材として用いたリチウム金属複合酸化物粉末を正極活物質（正極材料）に用いてコイン型電池を作成し、その電池評価を行った。
(Comparative Example 1)
A coin-type battery was prepared using the lithium metal composite oxide powder used as a base material in Example 1 as a positive electrode active material (positive electrode material), and the battery was evaluated.
（評価）
実施例１〜３の正極材料は、本発明に従って製造されたため、この正極材料を用いた非水系電解質二次電池は、初期放電容量が従来と変わらず大きく、かつ比較例に比べ正極界面抵抗が低いものとなっており、優れた特性を有した電池が得られることが確認された。
特に実施例３は、正極界面抵抗が良好である。
比較例１は、ランタンジルコニウム酸リチウムが混合されていないため、正極界面抵抗が高く、高出力化の要求に対応することは困難である。
以上の結果より、本発明の正極材料を用いた非水系電解質二次電池は、正極界面抵抗が低いものとなり、優れた特性を有した電池となることが確認できた。
(Evaluation)
Since the positive electrode materials of Examples 1 to 3 were manufactured according to the present invention, the non-aqueous electrolyte secondary battery using this positive electrode material has an initial discharge capacity that is as large as that of the prior art, and has a positive electrode interface resistance as compared with the comparative example. It was confirmed that a battery having low characteristics and excellent characteristics was obtained.
In particular, Example 3 has good positive electrode interface resistance.
In Comparative Example 1, since lithium lanthanum zirconate is not mixed, the positive electrode interface resistance is high, and it is difficult to meet the demand for higher output.
From the above results, it was confirmed that the non-aqueous electrolyte secondary battery using the positive electrode material of the present invention has a low positive electrode interface resistance and is a battery having excellent characteristics.
本発明の非水系電解質二次電池は、常に高容量を要求される小型携帯電子機器（ノート型パーソナルコンピュータや携帯電話端末など）の電源に好適であり、高出力が要求される電気自動車用電池にも好適である。
また、本発明の非水系電解質二次電池は、優れた安全性を有し、小型化、高出力化が可能であることから、搭載スペースに制約を受ける電気自動車用電源として好適である。
なお、本発明は、純粋に電気エネルギーで駆動する電気自動車用の電源のみならず、ガソリンエンジンやディーゼルエンジンなどの燃焼機関と併用するいわゆるハイブリッド車用の電源としても用いることができる。
The non-aqueous electrolyte secondary battery of the present invention is suitable for a power source of a small portable electronic device (such as a notebook personal computer or a mobile phone terminal) that always requires a high capacity, and an electric vehicle battery that requires a high output. Also suitable.
In addition, the nonaqueous electrolyte secondary battery of the present invention has excellent safety, and can be downsized and increased in output, and thus is suitable as a power source for an electric vehicle subject to restrictions on mounting space.
The present invention can be used not only as a power source for an electric vehicle driven purely by electric energy but also as a power source for a so-called hybrid vehicle used in combination with a combustion engine such as a gasoline engine or a diesel engine.
１ 正極（評価用電極）
２ 負極
３ セパレータ
４ ガスケット
５ ウェーブワッシャー
６ 正極缶
７ 負極缶
１０ コイン型電池
1 Positive electrode (Evaluation electrode)
2 Negative electrode 3 Separator 4 Gasket 5 Wave washer 6 Positive electrode can 7 Negative electrode can 10 Coin-type battery
Claims (12)
ランタンジルコニウム酸リチウム粉末と、
の混合物を含む、
ことを特徴とする非水系電解質二次電池用正極材料。 Formula Li z Ni 1-x-y Co x M y O 2 ( however, 0.01 ≦ x ≦ 0.35,0 ≦ y ≦ 0.35,0.97 ≦ z ≦ 1.20, M is added Element, at least one element selected from Mn, V, Mg, Mo, Nb, Ti and Al), and primary metal and secondary metal particles formed by agglomeration of primary particles Oxide powder,
Lanthanum lithium zirconate powder,
Including a mixture of
A positive electrode material for a non-aqueous electrolyte secondary battery.
ことを特徴とする請求項１に記載の非水系電解質二次電池用正極材料。 The lithium lanthanum zirconate powder contained in the positive electrode material has a particle size in the range of 0.01 to 0.5 μm.
The positive electrode material for a non-aqueous electrolyte secondary battery according to claim 1.
前記リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％である、
ことを特徴とする請求項１または２に記載の非水系電解質二次電池用正極材料。 The total amount of lanthanum and zirconium contained in the positive electrode material is
0.1 to 3.0 atomic% based on the total number of nickel, cobalt and M atoms contained in the lithium metal composite oxide powder,
The positive electrode material for a non-aqueous electrolyte secondary battery according to claim 1 or 2.
ことを特徴とする請求項１から３のいずれか１項に記載の非水系電解質二次電池用正極材料。 The lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 ,
The positive electrode material for a non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode material is a non-aqueous electrolyte secondary battery.
ことを特徴とする請求項１から４のいずれか１項に記載の非水系電解質二次電池用正極材料。 The positive electrode material further includes a non-aqueous organic solvent,
The positive electrode material for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, wherein the positive electrode material is a non-aqueous electrolyte secondary battery.
ことを特徴とする非水系電解質二次電池。 A positive electrode comprising the positive electrode material for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 5,
A non-aqueous electrolyte secondary battery.
ランタンジルコニウム酸リチウム粉末と、を混合する工程を含む、
ことを特徴とする非水系電解質二次電池用正極材料の製造方法。 Formula Li z Ni 1-x-y Co x M y O 2 ( however, 0.01 ≦ x ≦ 0.35,0 ≦ y ≦ 0.35,0.97 ≦ z ≦ 1.20, M is added Element, at least one element selected from Mn, V, Mg, Mo, Nb, Ti and Al), and primary metal and secondary metal particles formed by agglomeration of primary particles Oxide powder,
Including a step of mixing lithium lanthanum zirconate powder,
The manufacturing method of the positive electrode material for non-aqueous electrolyte secondary batteries characterized by the above-mentioned.
ことを特徴とする請求項７に記載の非水系電解質二次電池用正極材料の製造方法。 The lithium lanthanum zirconate powder has a particle size in the range of 0.01 to 0.5 μm.
The manufacturing method of the positive electrode material for nonaqueous electrolyte secondary batteries of Claim 7 characterized by the above-mentioned.
前記リチウム金属複合酸化物粉末を水洗する工程を含む、
ことを特徴とする請求項７または８に記載の非水系電解質二次電池用正極材料の製造方法。 Before the step of mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate,
Including a step of washing the lithium metal composite oxide powder with water.
The manufacturing method of the positive electrode material for nonaqueous electrolyte secondary batteries of Claim 7 or 8 characterized by the above-mentioned.
前記リチウム金属複合酸化物粉末に含まれるニッケル、コバルトおよびＭの原子数の合計に対して、０．１〜３．０原子％である、
ことを特徴とする請求項７から９のいずれか１項に記載の非水系電解質二次電池用正極材料の製造方法。 The total amount of lanthanum and zirconium contained in the positive electrode material is
0.1 to 3.0 atomic% based on the total number of nickel, cobalt and M atoms contained in the lithium metal composite oxide powder,
The manufacturing method of the positive electrode material for nonaqueous electrolyte secondary batteries of any one of Claim 7 to 9 characterized by the above-mentioned.
ことを特徴とする請求項７から１０のいずれか１項に記載の非水系電解質二次電池用正極材料の製造方法。 The lithium lanthanum zirconate is Li 7 La 3 Zr 2 O 12 ,
The manufacturing method of the positive electrode material for nonaqueous electrolyte secondary batteries of any one of Claims 7-10 characterized by the above-mentioned.
非水系有機溶剤を添加する、
ことを特徴とする請求項７から１１のいずれか１項に記載の非水系電解質二次電池用正極材料の製造方法。
In the step of mixing the lithium metal composite oxide powder and the lithium lanthanum zirconate,
Add non-aqueous organic solvent,
The manufacturing method of the positive electrode material for nonaqueous electrolyte secondary batteries of any one of Claims 7-11 characterized by the above-mentioned.
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