JP2016169145A - Perovskite type ion conductive oxide, complex and lithium secondary battery - Google Patents
Perovskite type ion conductive oxide, complex and lithium secondary battery Download PDFInfo
- Publication number
- JP2016169145A JP2016169145A JP2016043447A JP2016043447A JP2016169145A JP 2016169145 A JP2016169145 A JP 2016169145A JP 2016043447 A JP2016043447 A JP 2016043447A JP 2016043447 A JP2016043447 A JP 2016043447A JP 2016169145 A JP2016169145 A JP 2016169145A
- Authority
- JP
- Japan
- Prior art keywords
- conductive oxide
- ion conductive
- lithium
- perovskite
- perovskite type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- 229910052788 barium Inorganic materials 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 7
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 7
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 6
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 59
- 239000002131 composite material Substances 0.000 claims description 31
- 239000007784 solid electrolyte Substances 0.000 claims description 27
- 239000005486 organic electrolyte Substances 0.000 claims description 18
- 239000011149 active material Substances 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 2
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 claims description 2
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- -1 transition metal sulfides Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000004862 dioxolanes Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- ILPJNWCKZTZRJZ-UHFFFAOYSA-N 2,2,3,3-tetramethylthiolane 1,1-dioxide Chemical compound CC1(C)CCS(=O)(=O)C1(C)C ILPJNWCKZTZRJZ-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910020731 Li0.35La0.55TiO3 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 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
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910000314 transition metal 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、ペロブスカイト型イオン伝導性酸化物、複合体及びリチウム二次電池に関する。 The present invention relates to a perovskite type ion conductive oxide, a composite, and a lithium secondary battery.
従来、ペロブスカイト型イオン伝導性酸化物としては、Ｌｉ、Ｓｒ、Ｔａ及びＺｒを含む酸化物が提案されている（例えば、非特許文献１参照）。このペロブスカイト型酸化物は、３０℃での粒内伝導度σbが２×１０-4（Ｓ／ｃｍ）であり、粒界伝導度σgbが１×１０-4（Ｓ／ｃｍ）であり、トータルの伝導度σが７×１０-5（Ｓ／ｃｍ）であるとしている。また、ペロブスカイト型イオン伝導性酸化物としては、基本組成をＬｉ3/8Ｓｒ(7/16)Ｚｒ1/4Ｔａ3/4Ｏ3とし、パウダーベッドを用いて焼成したものが提案されている（例えば、非特許文献１参照）。このペロブスカイト型酸化物は、２７℃での粒内伝導度σbが３．５×１０-4（Ｓ／ｃｍ）であり、粒界伝導度σgbが９．５×１０-4（Ｓ／ｃｍ）であり、トータルの伝導度σが２．７×１０-4（Ｓ／ｃｍ）であるとしている。 Conventionally, oxides containing Li, Sr, Ta, and Zr have been proposed as perovskite ion conductive oxides (see, for example, Non-Patent Document 1). This perovskite oxide has an intragranular conductivity σb at 30 ° C. of 2 × 10 −4 (S / cm) and an intergranular conductivity σgb of 1 × 10 −4 (S / cm). The conductivity σ is 7 × 10 −5 (S / cm). Further, as the perovskite type ion conductive oxide, a basic composition of Li 3/8 Sr (7/16) Zr 1/4 Ta 3/4 O 3 and firing using a powder bed has been proposed. (For example, refer nonpatent literature 1). This perovskite oxide has an intragranular conductivity σb at 27 ° C. of 3.5 × 10 −4 (S / cm) and a grain boundary conductivity σgb of 9.5 × 10 −4 (S / cm). It is assumed that the total conductivity σ is 2.7 × 10 −4 (S / cm).
しかしながら、上述の非特許文献１のペロブスカイト型イオン伝導性酸化物では、イオン伝導性を有し、また、非特許文献２では、そのイオン伝導性をより向上してはいるものの、また十分でなく、さらなるイオン伝導性の向上が望まれていた。 However, the perovskite type ion conductive oxide of Non-Patent Document 1 described above has ionic conductivity, and Non-Patent Document 2 has improved the ionic conductivity, but is not sufficient. Further improvement of ion conductivity has been desired.
本発明は、このような課題に鑑みなされたものであり、イオン伝導性をより向上することができるペロブスカイト型イオン伝導性酸化物、複合体及びリチウム二次電池を提供することを主目的とする。 This invention is made | formed in view of such a subject, and it aims at providing the perovskite type ion conductive oxide, composite, and lithium secondary battery which can improve ion conductivity more. .
上述した目的を達成するために鋭意研究したところ、本発明者らは、Ｌｉ、Ｓｒ、Ｔａ及びＺｒを含むペロブスカイト型イオン伝導性酸化物のＳｒをＣａなどに置換すると、電気伝導度をより向上することができることを見いだし、本発明を完成するに至った。 As a result of diligent research to achieve the above-described object, the present inventors have improved the electrical conductivity by replacing Sr in the perovskite type ion conductive oxide containing Li, Sr, Ta and Zr with Ca or the like. It has been found that it can be done, and the present invention has been completed.
即ち、本発明のペロブスカイト型イオン伝導性酸化物は、
Ｌｉと、Ｓｒと、Ｚｒとを含み、
Ｃａ、Ｂａ、Ｍｇ、Ｓｃ、Ｙ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＬｎ（原子番号５７〜７１のランタノイド）のうち１種以上を含む元素Ａと、
Ｔａ、Ｎｂ、Ｗ、Ｍｏ、Ｒｅ、Ｒｕ及びＯｓのうち１種以上を含む元素Ｍと、を含むものである。
That is, the perovskite type ion conductive oxide of the present invention is
Li, Sr, and Zr,
An element A containing one or more of Ca, Ba, Mg, Sc, Y, Na, K, Rb, Cs and Ln (lanthanoids having an atomic number of 57 to 71);
And element M containing one or more of Ta, Nb, W, Mo, Re, Ru, and Os.
本発明の複合体は、上述したペロブスカイト型イオン伝導性酸化物を含む固体電解質層と、前記固体電解質層に隣接しリチウムを吸蔵放出する活物質を含む活物質層と、を備えたものである。あるいは、本発明の複合体は、上述したペロブスカイト型イオン伝導性酸化物を含む固体電解質層と、前記固体電解質層に隣接しリチウムイオンを伝導する有機電解質層と、を備えたものである。また、本発明のリチウム二次電池は、上述したいずれかの複合体を備えたものである。 The composite of the present invention comprises a solid electrolyte layer containing the perovskite ion conductive oxide described above, and an active material layer containing an active material adsorbing and releasing lithium adjacent to the solid electrolyte layer. . Or the composite_body | complex of this invention is equipped with the solid electrolyte layer containing the perovskite type ion conductive oxide mentioned above, and the organic electrolyte layer which adjoins the said solid electrolyte layer, and conducts lithium ion. Moreover, the lithium secondary battery of this invention is equipped with one of the composites mentioned above.
本発明のペロブスカイト型イオン伝導性酸化物、複合体及びリチウム二次電池は、イオン伝導性をより向上することができる。このような効果が得られる理由は、以下のように推測される。例えば、異種元素により置換されることにより、粒界の構造がイオン伝導を阻害しにくい構造になり、粒界での伝導度がより向上するためであると推察される。また、異種元素により置換されることにより、より最適化された格子定数を有する構造になり、粒内伝導度も上昇するためであると推察される。 The perovskite ion conductive oxide, composite and lithium secondary battery of the present invention can further improve ion conductivity. The reason why such an effect is obtained is presumed as follows. For example, it is presumed that the substitution at the grain boundary makes the structure of the grain boundary difficult to inhibit ionic conduction, and the conductivity at the grain boundary is further improved. Further, it is presumed that by substituting with a different element, the structure has a more optimized lattice constant and the intragranular conductivity increases.
本発明のペロブスカイト型イオン伝導性酸化物は、Ｌｉと、Ｓｒと、Ｚｒとを含み、Ｃａ、Ｂａ、Ｍｇ、Ｓｃ、Ｙ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＬｎ（原子番号５７〜７１のランタノイド）のうち１種以上を含む元素Ａと、Ｔａ、Ｎｂ、Ｗ、Ｍｏ、Ｒｅ、Ｒｕ及びＯｓのうち１種以上を含む元素Ｍと、を含むものである。 The perovskite type ion conductive oxide of the present invention contains Li, Sr, and Zr, and includes Ca, Ba, Mg, Sc, Y, Na, K, Rb, Cs, and Ln (lanthanoids having an atomic number of 57 to 71). ) And an element A containing at least one of Ta, Nb, W, Mo, Re, Ru, and Os.
このペロブスカイト型イオン伝導性酸化物は、基本構成をＳｒＺｒＯ3とするものとし、ＳｒサイトやＺｒサイトが他の元素により置換された、基本組成Ｌｉy□zＳｒ((1-y-z)(1-a))Ａa(1-y-z)Ｚｒ(1-x+a(m-2))Ｍ(x-a(m-2))Ｏ3で表されるものとしてもよい。図１は、ペロブスカイト型イオン伝導性酸化物の構造の一例を表す模式図である。このペロブスカイト型イオン伝導性酸化物において、基本組成式は、原料配合時の組成をいうものとしてもよい。この基本組成式において、元素Ａは、ペロブスカイト型酸化物のＳｒサイトに基本的に入る元素であり、Ｃａ、Ｂａ、Ｍｇ、Ｓｃ、Ｙ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＬｎ（原子番号５７〜７１のランタノイド）のうち１種以上の元素である。元素Ａは、Ｃａ、Ｂａ、Ｍｇ、Ｙ及びＬａのいずれか１以上であることが好ましく、Ｓｒのイオン半径に近いＣａやＢａ、Ｙ、Ｌａのうち１以上であることがより好ましい。この基本組成式において、元素Ｍは、ペロブスカイト型酸化物のＺｒサイトに基本的に入る元素であり、Ｔａ、Ｎｂ、Ｗ、Ｍｏ、Ｒｅ、Ｒｕ及びＯｓのうち１種以上の元素である。元素Ｍは、Ｚｒのイオン半径に近いＴａであることが好ましい。この基本組成式において、□は原子空孔である。また、この基本組成式において、ｘ，ｙ，ｚ，ａは、それぞれ０＜ｘ＜１、０＜ｙ＜１、０＜ａ＜１、ｘ（ｎ−４）＋ａ（１−ｙ−ｚ）（ｍ−２）＝ｙ＋２ｚ（但し、ｍはＡの価数であり、ｎはＭの価数）を満たす。この基本組成式において、元素Ａの係数ａは、０＜ａ≦０．１を満たすことが好ましく、ａ≦０．０５を満たすことがより好ましく、０．０２５≦ａ≦０．０５を満たすことが更に好ましい。係数ａが０＜ａ≦０．１を満たすと、電気伝導度がより向上し、好ましい。また、元素Ａは、Ｓｒと元素Ａとの全体に対して２ａｔ％以上１０ａｔ％以下の範囲でＳｒを置換していることが好ましく、５ａｔ％以下の範囲でＳｒを置換していることがより好ましく、２．５ａｔ％以上５ａｔ％以下の範囲でＳｒを置換していることが更に好ましい。このペロブスカイト型イオン伝導性酸化物は、基本組成Ｌｉ3/8□3/16Ｓｒ(7(1-a)/16)Ｃａ7a/16Ｚｒ1/4Ｔａ3/4Ｏ3（式中、□は原子空孔であり、０＜ａ≦０．１を満たす）で表されるものとしてもよい。また、このペロブスカイト型イオン伝導性酸化物は、基本組成Ｌｉ3/8□3/16Ｓｒ(7(1-a)/16)Ｌａ7a/16Ｚｒ(1/4+7a/16)Ｔａ(3/4-7a/16)Ｏ3（式中、□は原子空孔であり、０＜ａ≦０．１を満たす）で表されるものとしてもよい。 This perovskite type ion conductive oxide has a basic composition of SrZrO 3, and a basic composition Li y □ z Sr ((1-yz) (1- a)) A a (1-yz) Zr (1-x + a (m-2)) M (xa (m-2)) O 3 FIG. 1 is a schematic diagram showing an example of the structure of a perovskite type ion conductive oxide. In this perovskite ion conductive oxide, the basic composition formula may refer to a composition at the time of blending raw materials. In this basic composition formula, the element A is an element that basically enters the Sr site of the perovskite oxide, and includes Ca, Ba, Mg, Sc, Y, Na, K, Rb, Cs, and Ln (atomic number 57 to 71 lanthanoids). The element A is preferably any one or more of Ca, Ba, Mg, Y, and La, and more preferably one or more of Ca, Ba, Y, and La that are close to the ionic radius of Sr. In this basic composition formula, the element M is an element that basically enters the Zr site of the perovskite oxide, and is one or more elements of Ta, Nb, W, Mo, Re, Ru, and Os. The element M is preferably Ta close to the ionic radius of Zr. In this basic composition formula, □ is an atomic vacancy. In this basic composition formula, x, y, z, and a are 0 <x <1, 0 <y <1, 0 <a <1, x (n−4) + a (1−yz), respectively. (M−2) = y + 2z (where m is the valence of A and n is the valence of M). In this basic composition formula, the coefficient a of the element A preferably satisfies 0 <a ≦ 0.1, more preferably satisfies a ≦ 0.05, and satisfies 0.025 ≦ a ≦ 0.05. Is more preferable. When the coefficient a satisfies 0 <a ≦ 0.1, the electrical conductivity is further improved, which is preferable. The element A preferably substitutes Sr in a range of 2 at% to 10 at% with respect to the whole of Sr and the element A, and more preferably substitutes Sr in a range of 5 at% or less. Preferably, Sr is more preferably substituted in the range of 2.5 at% or more and 5 at% or less. This perovskite ion conductive oxide has a basic composition of Li 3/8 □ 3/16 Sr (7 (1-a) / 16) Ca 7a / 16 Zr 1/4 Ta 3/4 O 3 (where □ Is an atomic vacancy, and may be represented by 0 <a ≦ 0.1. This perovskite type ion conductive oxide has a basic composition of Li 3/8 □ 3/16 Sr (7 (1-a) / 16) La 7a / 16 Zr (1/4 + 7a / 16) Ta (3 / 4-7a / 16) O 3 (wherein □ is an atomic vacancy and satisfies 0 <a ≦ 0.1).
ここで、ペロブスカイト型イオン伝導性酸化物は、主としてペロブスカイト型の構造を有していればよく、例えば、酸化物に他の構造が一部含まれていたり、例えばＸ線回折のピーク位置がシフトしている、回折の主相が正方晶、立方晶、斜方晶などペロブスカイトからみて歪んだ構造を含むものとする。また、組成式で示しているが、酸化物には他の元素や構造などが一部含まれていてもよい。なお、「基本組成」とは、Ａ，Ｍにはそれぞれ主成分の元素と１以上の副成分の元素を含んでいてもよい趣旨である。 Here, the perovskite type ion conductive oxide only needs to have mainly a perovskite type structure. For example, the oxide may include a part of other structure, or the peak position of X-ray diffraction may be shifted, for example. It is assumed that the main phase of diffraction includes a distorted structure as seen from the perovskite, such as tetragonal, cubic and orthorhombic. In addition, although shown in the composition formula, the oxide may partially include other elements, structures, and the like. The “basic composition” means that each of A and M may contain a main component element and one or more subcomponent elements.
本発明のペロブスカイト型イオン伝導性酸化物は、電気伝導度σ（２５℃）が７．０×１０-5（Ｓ／ｃｍ）以上であることが好ましく、１．０×１０-4（Ｓ／ｃｍ）以上であることがより好ましく、２．０×１０-4（Ｓ／ｃｍ）以上であることが更に好ましい。また、本発明のペロブスカイト型イオン伝導性酸化物は、粒界部での電気伝導度σgb（２５℃）が２．０×１０-4（Ｓ／ｃｍ）以上であることが好ましく、５．０×１０-4（Ｓ／ｃｍ）以上であることがより好ましく、６．０×１０-4（Ｓ／ｃｍ）以上であることが更に好ましい。また、本発明のペロブスカイト型イオン伝導性酸化物は、粒内（バルク）での電気伝導度σb（２５℃）が８．０×１０-5（Ｓ／ｃｍ）以上であることが好ましく、３．０×１０-4（Ｓ／ｃｍ）以上であることがより好ましく、４．０×１０-4（Ｓ／ｃｍ）以上であることが更に好ましい。これらの電気伝導度σ，σb，σgbは、Ｌｉ、元素Ａ，元素Ｍの添加割合（ａ，ｘ，ｙ，ｚ）や、焼成温度を調整することにより、適宜変更することができる。 The perovskite ion conductive oxide of the present invention preferably has an electric conductivity σ (25 ° C.) of 7.0 × 10 −5 (S / cm) or more, and 1.0 × 10 −4 (S / cm). cm) or more, more preferably 2.0 × 10 −4 (S / cm) or more. The perovskite type ion conductive oxide of the present invention preferably has an electric conductivity σgb (25 ° C.) at the grain boundary portion of 2.0 × 10 −4 (S / cm) or more. It is more preferably at least 10 −4 (S / cm) and even more preferably at least 6.0 × 10 −4 (S / cm). In the perovskite type ion conductive oxide of the present invention, the electrical conductivity σb (25 ° C.) in the grains (bulk) is preferably 8.0 × 10 −5 (S / cm) or more. .0 × 10 -4 more preferably (S / cm) or more, more preferably 4.0 × 10 -4 (S / cm ) or more. These electrical conductivities σ, σb, and σgb can be appropriately changed by adjusting the addition ratio (a, x, y, z) of Li, element A, and element M, and the firing temperature.
本発明のペロブスカイト型イオン伝導性酸化物は、活性化エネルギーＥａが４０（ｋＪ／ｍｏｌ）より小さいことが好ましく、３５（ｋＪ／ｍｏｌ）以下であることがより好ましく、３３（ｋＪ／ｍｏｌ）以下であることが更に好ましい。活性化エネルギーＥａが４０（ｋＪ／ｍｏｌ）より小さいと、イオン伝導性がより好ましい。この活性化エネルギーＥａは、Ｌｉ、元素Ａ，元素Ｍの添加割合（ａ，ｘ，ｙ，ｚ）や、焼成温度を調整することにより、適宜変更することができる。 In the perovskite type ion conductive oxide of the present invention, the activation energy Ea is preferably less than 40 (kJ / mol), more preferably 35 (kJ / mol) or less, and 33 (kJ / mol) or less. More preferably. When the activation energy Ea is smaller than 40 (kJ / mol), ion conductivity is more preferable. This activation energy Ea can be appropriately changed by adjusting the addition ratio (a, x, y, z) of Li, element A, and element M, and the firing temperature.
本発明のペロブスカイト型イオン伝導性酸化物は、１５００℃以下で焼成されていることが好ましく、１４００℃以下で焼成されていることがより好ましく、１３５０℃以下で焼成されていることが更に好ましい。１５００℃以下の焼成では、焼成エネルギーの低減をより図ることができる。ペロブスカイト型構造を形成する観点から、ペロブスカイト型イオン伝導性酸化物は、９００℃以上で焼成されていることが好ましい。 The perovskite ion conductive oxide of the present invention is preferably fired at 1500 ° C. or less, more preferably 1400 ° C. or less, and still more preferably 1350 ° C. or less. In firing at 1500 ° C. or lower, the firing energy can be further reduced. From the viewpoint of forming a perovskite structure, the perovskite ion conductive oxide is preferably fired at 900 ° C. or higher.
本発明のペロブスカイト型イオン伝導性酸化物は、リチウム二次電池に利用することができる。リチウムイオン伝導度がより高められているからである。このペロブスカイト型イオン伝導性酸化物は、例えば、リチウム二次電池の固体電解質として利用するものとしてもよいし、リチウム二次電池のセパレータとして利用するものとしてもよい。こうしたリチウム二次電池は、リチウムを吸蔵・放出しうる正極活物質を有する正極と、リチウムを吸蔵・放出しうる負極活物質を有する負極との間に、本発明のペロブスカイト型イオン伝導性酸化物を介在させた構成とすることができる。正極に用いる正極活物質としては、遷移金属元素を含む硫化物や、リチウムと遷移金属元素とを含む酸化物などを用いることができる。具体的には、ＴｉＳ2、ＴｉＳ3、ＭｏＳ3、ＦｅＳ2などの遷移金属硫化物、基本組成式をＬｉ(1-m)ＭｎＯ2（０＜ｍ＜１など、以下同じ）やＬｉ(1-m)Ｍｎ2Ｏ4などとするリチウムマンガン複合酸化物、基本組成式をＬｉ(1-m)ＣｏＯ2などとするリチウムコバルト複合酸化物、基本組成式をＬｉ(1-m)ＮｉＯ2などとするリチウムニッケル複合酸化物、基本組成式をＬｉ(1-m)ＮｉaＭｎbＯ2（ａ＋ｂ＝１）などとするリチウムニッケルマンガン複合酸化物、基本組成式をＬｉ(1-m)ＮｉaＣｏbＭｎcＯ2（ａ＋ｂ＋ｃ＝１）などとするリチウムニッケルコバルトマンガン複合酸化物、基本組成式をＬｉＶ2Ｏ3などとするリチウムバナジウム複合酸化物、Ｖ2Ｏ5などの遷移金属酸化物などを用いることができる。これらのうち、リチウムの遷移金属複合酸化物、例えば、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎＯ2、ＬｉＶ2Ｏ3などが好ましい。また、負極に用いる負極活物質としては、リチウム、リチウム合金、スズ化合物などの無機化合物、リチウムイオンを吸蔵・放出可能な炭素質材料、基本組成式をＬｉ4Ｔｉ5Ｏ12などとするリチウムチタン複合酸化物及び導電性ポリマーなどが挙げられる。炭素質材料は、特に限定されるものではないが、コークス類、ガラス状炭素類、グラファイト類、難黒鉛化性炭素類、熱分解炭素類、炭素繊維などが挙げられる。このうち、人造黒鉛、天然黒鉛などのグラファイト類が、金属リチウムに近い作動電位を有し、高い作動電圧での充放電が可能であるため、好ましい。 The perovskite type ion conductive oxide of the present invention can be used for a lithium secondary battery. This is because the lithium ion conductivity is further increased. This perovskite type ion conductive oxide may be used, for example, as a solid electrolyte of a lithium secondary battery, or may be used as a separator of a lithium secondary battery. Such a lithium secondary battery includes a perovskite ion conductive oxide according to the present invention between a positive electrode having a positive electrode active material capable of inserting and extracting lithium and a negative electrode having a negative electrode active material capable of inserting and extracting lithium. It can be set as the structure which intervened. As a positive electrode active material used for the positive electrode, a sulfide containing a transition metal element, an oxide containing lithium and a transition metal element, or the like can be used. Specifically, transition metal sulfides such as TiS 2 , TiS 3 , MoS 3 , and FeS 2, and the basic composition formula are Li (1-m) MnO 2 (0 <m <1, etc., the same shall apply hereinafter) and Li (1 -m) Lithium-manganese composite oxides such as Mn 2 O 4, lithium cobalt composite oxides whose basic composition formula is Li (1-m) CoO 2, etc., basic composition formulas such as Li (1-m) NiO 2 Lithium-nickel composite oxide, with a basic composition formula of Li (1-m) Ni a Mn b O 2 (a + b = 1), etc., and a basic composition formula of Li (1-m) Ni a Co b Mn c O 2 ( a + b + c = 1) lithium-nickel-cobalt-manganese composite oxide, and the like, lithium vanadium composite oxide, and the like LiV 2 O 3 the basic formula, the transition metal oxide such as V 2 O 5 Etc. can be used. Of these, lithium transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , and LiV 2 O 3 are preferable. Moreover, as a negative electrode active material used for a negative electrode, lithium titanium which uses inorganic compounds, such as lithium, a lithium alloy, a tin compound, a carbonaceous material which can occlude / release lithium ions, and a basic composition formula such as Li 4 Ti 5 O 12 Examples include composite oxides and conductive polymers. The carbonaceous material is not particularly limited, and examples thereof include cokes, glassy carbons, graphites, non-graphitizable carbons, pyrolytic carbons, and carbon fibers. Of these, graphites such as artificial graphite and natural graphite are preferable because they have an operating potential close to that of metallic lithium and can be charged and discharged at a high operating voltage.
また、本発明のリチウム二次電池は、複合体を備えているものとしてもよい。複合体は、固体電解質層と活物質層とが積層されているものとしてもよいし、固体電解質層と有機電解質とを有するものとしてもよい。この有機電解質の表面には、固体電解質層が隣接されているものとしてもよい。有機電解質は、例えば、リチウムを含む支持塩と有機物とを含むものとしてもよい。支持塩としては、例えば、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＳｂＦ6、ＬｉＳｉＦ6、ＬｉＡｌＦ4、ＬｉＳＣＮ、ＬｉＣｌＯ4、ＬｉＣｌ、ＬｉＦ、ＬｉＢｒ、ＬｉＩ、ＬｉＡｌＣｌ4などが挙げられる。また、有機物は、有機溶媒などの液体としてもよいし、有機高分子化合物などの固体としてもよい。有機溶媒としては、例えば、カーボネート類、エステル類、エーテル類、ニトリル類、フラン類、スルホラン類及びジオキソラン類などが挙げられ、これらを単独又は混合して用いることができる。カーボネート類としては、例えば、エチレンカーボネートやプロピレンカーボネートなどの環状カーボネート類や、ジメチルカーボネート、エチルメチルカーボネートなどの鎖状カーボネート類が挙げられる。また、γ−ブチルラクトンなどの環状エステル類、酢酸メチルなどの鎖状エステル類、ジメトキシエタンなどのエーテル類、アセトニトリルなどのニトリル類、テトラヒドロフランなどのフラン類、テトラメチルスルホランなどのスルホラン類、１，３−ジオキソランなどのジオキソラン類などが挙げられる。有機高分子化合物としては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリアセトニトリル、ポリフッ化ビニリデン、ポリアクリロニトリル、ポリメチルメタクリレート、ポリビニルアセテート、ポリビニルピロリドンなどが挙げられる。有機電解質は、ポリマーと支持塩とで構成されるポリマーゲルが好ましい。 Moreover, the lithium secondary battery of the present invention may include a composite. The composite may be formed by laminating a solid electrolyte layer and an active material layer, or may have a solid electrolyte layer and an organic electrolyte. A solid electrolyte layer may be adjacent to the surface of the organic electrolyte. The organic electrolyte may include, for example, a supporting salt containing lithium and an organic substance. Examples of the supporting salt include LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiSbF 6 , LiSiF 6 , LiAlF 4 , LiSCN, Examples include LiClO 4 , LiCl, LiF, LiBr, LiI, and LiAlCl 4 . Further, the organic substance may be a liquid such as an organic solvent or a solid such as an organic polymer compound. Examples of the organic solvent include carbonates, esters, ethers, nitriles, furans, sulfolanes and dioxolanes, and these can be used alone or in combination. Examples of the carbonates include cyclic carbonates such as ethylene carbonate and propylene carbonate, and chain carbonates such as dimethyl carbonate and ethyl methyl carbonate. In addition, cyclic esters such as γ-butyllactone, chain esters such as methyl acetate, ethers such as dimethoxyethane, nitriles such as acetonitrile, furans such as tetrahydrofuran, sulfolanes such as tetramethylsulfolane, 1, And dioxolanes such as 3-dioxolane. Examples of the organic polymer compound include polyethylene oxide, polypropylene oxide, polyacetonitrile, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, and polyvinylpyrrolidone. The organic electrolyte is preferably a polymer gel composed of a polymer and a supporting salt.
リチウム二次電池の構造は、特に限定されないが、例えば図２に示す構造が挙げられる。図２は、全固体型リチウム二次電池１０の構造の一例を示す説明図である。この全固体型リチウム二次電池は、上述したペロブスカイト型イオン伝導性酸化物を含む固体電解質層１１と、この固体電解質層１１の一方の面に形成されリチウムを吸蔵放出する正極活物質を含む正極活物質層１３と、この固体電解質層１１の他方の面に形成されリチウムを吸蔵放出する負極活物質を含む負極活物質層１６とを有する。正極活物質層１３の表面には、集電体１４が形成されており、負極活物質層１６の表面には、集電体１７が形成されている。この全固体型リチウム二次電池１０は、固体電解質層１１及び正極活物質層１３が複合体２０であり、固体電解質層１１及び負極活物質層１６が複合体２１であるものとしてもよい。あるいは、リチウム二次電池の構造は、図３に示すように、固体電解質層１１及び有機電解質層１８を有する複合体２２と、固体電解質層１１及び有機電解質層１９を有する複合体２３と、を備えたものとしてもよい。図３は、全固体型リチウム二次電池１０Ｂの構造の一例を示す説明図である。有機電解質層１８には、正極活物質層１３が隣接され、有機電解質層１９には負極活物質層１６が隣接されている。この有機電解質層１８，１９はセパレータとして機能するものとしてもよい。 Although the structure of a lithium secondary battery is not specifically limited, For example, the structure shown in FIG. 2 is mentioned. FIG. 2 is an explanatory diagram showing an example of the structure of the all solid-state lithium secondary battery 10. This all solid-state lithium secondary battery includes a solid electrolyte layer 11 containing the perovskite ion conductive oxide described above, and a positive electrode containing a positive electrode active material that is formed on one surface of the solid electrolyte layer 11 and occludes and releases lithium. It has an active material layer 13 and a negative electrode active material layer 16 that is formed on the other surface of the solid electrolyte layer 11 and contains a negative electrode active material that absorbs and releases lithium. A current collector 14 is formed on the surface of the positive electrode active material layer 13, and a current collector 17 is formed on the surface of the negative electrode active material layer 16. In the all solid-state lithium secondary battery 10, the solid electrolyte layer 11 and the positive electrode active material layer 13 may be a composite 20, and the solid electrolyte layer 11 and the negative electrode active material layer 16 may be a composite 21. Alternatively, as shown in FIG. 3, the structure of the lithium secondary battery includes a composite 22 having the solid electrolyte layer 11 and the organic electrolyte layer 18 and a composite 23 having the solid electrolyte layer 11 and the organic electrolyte layer 19. It may be provided. FIG. 3 is an explanatory diagram showing an example of the structure of the all solid-state lithium secondary battery 10B. The organic electrolyte layer 18 is adjacent to the positive electrode active material layer 13, and the organic electrolyte layer 19 is adjacent to the negative electrode active material layer 16. The organic electrolyte layers 18 and 19 may function as a separator.
以上詳述したペロブスカイト型イオン伝導性酸化物は、イオン伝導性をより向上することができる。このような効果が得られる理由は、例えば、異種元素に置換されることにより、粒界の構造がイオン伝導を阻害しにくい構造になり、粒界での伝導度がより向上するためであると推察される。また、異種元素により置換されることにより、より最適化された格子定数を有する構造になり、粒内伝導度も上昇するためであると推察される。 The perovskite type ion conductive oxide described in detail above can further improve the ion conductivity. The reason why such an effect is obtained is that, for example, by substituting with a different element, the structure of the grain boundary becomes a structure that does not hinder ion conduction, and the conductivity at the grain boundary is further improved. Inferred. Further, it is presumed that by substituting with a different element, the structure has a more optimized lattice constant and the intragranular conductivity increases.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
以下では、Ｓｒサイトを他の元素で置換したペロブスカイト型イオン伝導性酸化物を具体的に合成した例を、実験例として説明する。 Below, the example which specifically synthesize | combined the perovskite type ion conductive oxide which substituted the Sr site with the other element is demonstrated as an experiment example.
［ペロブスカイト型酸化物の作製］
ＳｒサイトをＣａ、Ｙ、Ｍｇ、Ｌａ及びＢａで置換したペロブスカイト型イオン伝導性酸化物Ｌｉ3/8□3/16Ｓｒ(7(1-a)/16)Ａ7a/16Ｚｒ1/4Ｔａ3/4Ｏ3（□は原子空孔であり、ＡはＣａ、Ｙ、Ｍｇ、Ｌａ及びＢａのいずれか、ａ＝０．０２５）を合成した。このペロブスカイト型イオン伝導性酸化物は、Ｌｉ2ＣＯ3、ＳｒＣＯ3、ＺｒＯ2、Ｔａ2Ｏ5及びＡ原料を出発原料に用いて合成を行った。Ａ原料は、ＣａＣＯ3、Ｙ2Ｏ3、ＭｇＯ、Ｌａ2Ｏ3及びＢａＣＯ3とした。はじめに、出発原料を化学量論比になるように秤量し、エタノール中にてボールミル（３００ｒｐｍ／ジルコニアボール）で３００分、混合・粉砕を行った。出発原料の混合粉末をボールとエタノールから分離したのち、Ａｌ2Ｏ3製のるつぼ中にて、１１００℃、１２時間、大気雰囲気で仮焼を行った。次に、仮焼した粉体をペレット状に３００ＭＰａでＣＩＰ成型し、パウダーベッドを用いて本焼成した。本焼成は、仮焼粉体をパウダーベッドとして入れたＡｌ2Ｏ3製のるつぼ中にこのペレット成形体を入れ、固相反応法により、１３００℃、１５時間、大気中の条件下で行った。Ｓｒサイトを置換しないものを実験例１とし、Ｓｒサイトを置換して得られた試料をそれぞれ実験例２〜６とした。
[Preparation of perovskite oxide]
Perovskite-type ion conductive oxide with Sr site substituted by Ca, Y, Mg, La and Ba Li 3/8 □ 3/16 Sr (7 (1-a) / 16) A 7a / 16 Zr 1/4 Ta 3/4 O 3 (□ is an atomic vacancy, A is any one of Ca, Y, Mg, La and Ba, a = 0.025) was synthesized. The perovskite ion conductive oxide was synthesized using Li 2 CO 3 , SrCO 3 , ZrO 2 , Ta 2 O 5 and A raw materials as starting materials. The A raw material was CaCO 3 , Y 2 O 3 , MgO, La 2 O 3 and BaCO 3 . First, starting materials were weighed so as to have a stoichiometric ratio, and mixed and pulverized in ethanol in a ball mill (300 rpm / zirconia balls) for 300 minutes. After the mixed powder of the starting material was separated from the balls and ethanol, it was calcined in an air atmosphere at 1100 ° C. for 12 hours in an Al 2 O 3 crucible. Next, the calcined powder was CIP-molded into a pellet at 300 MPa and subjected to main firing using a powder bed. The main calcination was performed by placing the pellet compact in an Al 2 O 3 crucible containing a calcined powder as a powder bed, and at 1300 ° C. for 15 hours under atmospheric conditions by a solid phase reaction method. . Samples obtained by substituting the Sr sites were those obtained by substituting the Sr sites for Experimental Examples 1 and 6, respectively.
ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物Ｌｉ3/8□3/16Ｓｒ(7(1-a)/16)Ｃａ7a/16Ｚｒ1/4Ｔａ3/4Ｏ3（□は原子空孔であり、０≦ａ≦０．２）を合成した。このペロブスカイト型イオン伝導性酸化物は、Ｌｉ2ＣＯ3、ＳｒＣＯ3、ＺｒＯ2、Ｔａ2Ｏ5及びＣａＣＯ3を出発原料に用いて合成を行った。ここで、実験例１、２、７〜１０は、それぞれａ＝０、０．０２５、０．０３７５、０．０５、０．１、０．２とし（表１参照）、実験例１と同様の工程を行い作製した。 Perovskite-type ion-conductive oxide with Sr site substituted by Ca Li 3/8 □ 3/16 Sr (7 (1-a) / 16) Ca 7a / 16 Zr 1/4 Ta 3/4 O 3 (□ is Atomic vacancies, 0 ≦ a ≦ 0.2) were synthesized. The perovskite type ion conductive oxide was synthesized using Li 2 CO 3 , SrCO 3 , ZrO 2 , Ta 2 O 5 and CaCO 3 as starting materials. Here, in Experimental Examples 1, 2, 7 to 10, a = 0, 0.025, 0.0375, 0.05, 0.1, and 0.2 (see Table 1), respectively, and the same as Experimental Example 1 This process was performed.
ＳｒサイトをＬａで置換したペロブスカイト型イオン伝導性酸化物Ｌｉ3/8□3/16Ｓｒ(7(1-a)/16)Ｌａ7a/16Ｚｒ(1/4+7a/16)Ｔａ(3/4-7a/16)Ｏ3（式中、□は原子空孔であり、０≦ａ≦０．１を満たす）を合成した。このペロブスカイト型イオン伝導性酸化物は、Ｌｉ2ＣＯ3、ＳｒＣＯ3、ＺｒＯ2、Ｔａ2Ｏ5及びＬａ2Ｏ3を出発原料に用いて合成を行った。ここで、実験例５、１１、１２は、それぞれａ＝０．０２５、０．０５、０．１とし（表２参照）、実験例１と同様の工程を行い作製した。 Perovskite type ion conductive oxide with Sr site substituted by La 3/8 □ 3/16 Sr (7 (1-a) / 16) La 7a / 16 Zr (1/4 + 7a / 16) Ta (3 / 4-7a / 16) O 3 (wherein □ is an atomic vacancy and satisfies 0 ≦ a ≦ 0.1) was synthesized. This perovskite type ion conductive oxide was synthesized using Li 2 CO 3 , SrCO 3 , ZrO 2 , Ta 2 O 5 and La 2 O 3 as starting materials. Here, in Experimental Examples 5, 11, and 12, a = 0.025, 0.05, and 0.1 were set, respectively (see Table 2), and the same steps as in Experimental Example 1 were performed.
（Ｘ線回折測定）
Ｘ線回折測定（ＸＲＤ）は、ＸＲＤ測定器（リガク製、Ｓｍａｒｔ−Ｌａｂ）を用いて、集中法型光学系で試料粉末をＣｕＫα、２θ：１０〜８０°，５°／ｍｉｎの条件で測定した。結晶構造解析は、結晶構造解析用プログラム：Ｒｉｅｔａｎ−２０００（Ｍａｔｅｒ． Ｓｃｉ． Ｆｏｒｕｍ， ｐ３２１−３２４（２０００），１９８）を用いて解析を行った。。図２は、実験例１〜６のＸ線回折測定結果である。図３は、実験例１、２、８〜１０のＸ線回折測定結果である。図２に示すように、いくつかの試料では異相（ＬｉＴａＯ3）が認められたものの、実験例１〜６では、回折線がシフトしており、ＬＳＴＺのＳｒサイトに各元素が置換されているものと認められた。また、図３に示すように、ＳｒをＣａで置換した実験例２、８〜１０は、おおむね単相であった。また、Ｃａの置換量を増加させるのに従い、ペロブスカイト構造由来の回折線が高角側にシフトした。ペロブスカイト構造のＳｒ（イオン半径＝１．４４Å）にＣａ（イオン半径＝１．３４Å）が置換されて入り込んだものと推察された。
(X-ray diffraction measurement)
X-ray diffraction measurement (XRD) is performed by using a XRD measuring device (manufactured by Rigaku, Smart-Lab) and measuring the sample powder under the conditions of CuKα, 2θ: 10 to 80 °, 5 ° / min with a concentrated optical system. did. Crystal structure analysis was performed using a crystal structure analysis program: Rietan-2000 (Matter. Sci. Forum, p321-324 (2000), 198). . FIG. 2 shows the X-ray diffraction measurement results of Experimental Examples 1 to 6. FIG. 3 shows the X-ray diffraction measurement results of Experimental Examples 1, 2, and 8 to 10. As shown in FIG. 2, although a heterogeneous phase (LiTaO 3 ) was observed in some samples, the diffraction lines were shifted in Experimental Examples 1 to 6, and each element was substituted at the Sr site of LSTZ. It was accepted. Moreover, as shown in FIG. 3, Experimental Examples 2 and 8 to 10 in which Sr was replaced with Ca were generally single phase. Further, as the Ca substitution amount was increased, the diffraction lines derived from the perovskite structure shifted to the high angle side. It was inferred that Ca (ion radius = 1.34Å) was substituted for Sr (ion radius = 1.44Å) of the perovskite structure.
（電気伝導度測定）
伝導度は、恒温槽中にてＡＣインピーダンスアナライザー（Ａｇｉｌｅｎｔ４２９４Ａ）を用い、周波数４０Ｈｚ〜１１０ＭＨｚ、振幅電圧１００ｍＶの条件で、ナイキストプロットの円弧より抵抗値を求め、この抵抗値から算出した。伝導度σは、σ＝１／ＲTotal，ＲTotal＝Ｒb＋Ｒgbの式から算出した。試料は、直径１１．７ｍｍ×厚さ０．２ｍｍのサイズとした。ＡＣインピーダンスアナライザーで測定する際のブロッキング電極にはＡｕ電極を用いた。Ａｕ電極は市販のＡｕペーストを８５０℃、３０分の条件で焼き付けることで形成した。図４は、実験例１〜６のナイキストプロットである。図５は、実験例２、８〜１０のナイキストプロットである。実験例１、２、７〜１０の２５℃での伝導度を表１に示す。実験例１、５、１１、１２の２５℃での伝導度を表２に示す。図６は、実験例１、２、７〜１０のアレニウスプロット及びＣａドープ量に対する伝導度の関係図である。図７は、実験例１、５、１１、１２のアレニウスプロット及びＬａドープ量に対する伝導度の関係図である。
(Electrical conductivity measurement)
The conductivity was calculated from a resistance value obtained from an arc of the Nyquist plot using an AC impedance analyzer (Agilent 4294A) in a thermostatic chamber under conditions of a frequency of 40 Hz to 110 MHz and an amplitude voltage of 100 mV. The conductivity σ was calculated from the equation: σ = 1 / R Total and R Total = R b + R gb . The sample had a size of diameter 11.7 mm × thickness 0.2 mm. An Au electrode was used as a blocking electrode when measuring with an AC impedance analyzer. The Au electrode was formed by baking a commercially available Au paste at 850 ° C. for 30 minutes. FIG. 4 is a Nyquist plot of Experimental Examples 1-6. FIG. 5 is a Nyquist plot of Experimental Examples 2 and 8-10. Table 1 shows the conductivities of Experimental Examples 1, 2, and 7 to 10 at 25 ° C. Table 2 shows the conductivities of Experimental Examples 1, 5, 11, and 12 at 25 ° C. FIG. 6 is an Arrhenius plot of Experimental Examples 1, 2, and 7 to 10 and a relationship diagram of conductivity with respect to the Ca doping amount. FIG. 7 is an Arrhenius plot of Experimental Examples 1, 5, 11, and 12, and a relationship diagram of conductivity with respect to the La doping amount.
図４に示すように、実験例１〜６では、ドープ量の関係で粒内（バルク）の電気伝導度σbは大きな変化がなかった。また、ＳｒをＣａやＬａで置換したものは、粒界部での電気伝導度σgbが顕著に低くなることがわかった。図５及び表１に示すように、Ｓｒを一部Ｃａに置換した実験例２〜４（０＜ａ（ａｔ％）≦１０）では、粒界部での電気伝導度σgb（２５℃）がＣａに置換しない実験例１（ａ＝０であるＬｉ3/8Ｓｒ7/16Ｚｒ1/4Ｔａ3/4Ｏ3）に対して向上していることがわかった。また、Ｃａに置換した実験例２、３では、粒内の電気伝導度σb（２５℃）が実験例１以上の値を示した。各試料の相対密度は９６〜９９％であったことから、伝導度がａ値に応じて変化するのは、密度による影響ではないと考えられた。また、表２に示すように、Ｓｒを一部Ｌａに置換した実験例５、１１、１２（０＜ａ（ａｔ％）≦１０）では、粒界部での電気伝導度σgb（２５℃）が実験例１（ａ＝０であるＬｉ3/8Ｓｒ7/16Ｚｒ1/4Ｔａ3/4Ｏ3）に対して向上していることがわかった。また、Ｌａに置換した実験例５、１１、１２では、粒内の電気伝導度σb（２５℃）が実験例１と同等の値を示した。 As shown in FIG. 4, in Experimental Examples 1 to 6, the intra-granular (bulk) electrical conductivity σb did not change greatly due to the doping amount. Further, it was found that when Sr was substituted with Ca or La, the electrical conductivity σgb at the grain boundary portion was remarkably lowered. As shown in FIG. 5 and Table 1, in Experimental Examples 2 to 4 (0 <a (at%) ≦ 10) in which Sr is partially replaced with Ca, the electrical conductivity σgb (25 ° C.) at the grain boundary part is It turned out that it is improving with respect to Experimental example 1 which does not substitute for Ca (Li 3/8 Sr 7/16 Zr 1/4 Ta 3/4 O 3 where a = 0). Further, in Experimental Examples 2 and 3 in which Ca was substituted, the electrical conductivity σb (25 ° C.) in the grains showed a value higher than that of Experimental Example 1. Since the relative density of each sample was 96 to 99%, it was considered that the change in conductivity according to the a value was not an influence of the density. Further, as shown in Table 2, in Experimental Examples 5, 11, and 12 (0 <a (at%) ≦ 10) in which Sr is partially replaced with La, the electrical conductivity σgb (25 ° C.) at the grain boundary part Was found to be improved over Experimental Example 1 (Li 3/8 Sr 7/16 Zr 1/4 Ta 3/4 O 3 where a = 0). Further, in Experimental Examples 5, 11, and 12 in which La was substituted, the intra-grain electrical conductivity σb (25 ° C.) showed a value equivalent to that of Experimental Example 1.
（活性化エネルギー（Ｅａ））
活性化エネルギーＥａ（ｋＪ／ｍｏｌ）はアレニウス（Ａｒｒｈｅｎｉｕｓ）の式：σ＝Ａｅｘｐ（−Ｅａ／ｋＴ）（σ：伝導度、Ａ：頻度因子、ｋ：ボルツマン定数、Ｔ：絶対温度）を用い、アレニウスプロットの傾きより求めた。求めた結果を表１、２に示す。Ｃａ置換量ａ（ａｔ％）が２以上１０以下の範囲では、より低い活性化エネルギー（Ｅａ）を示し、５ａｔ％以下では更に低い値を示した。また、Ｌａ置換量ａ（ａｔ％）が２以上１０以下の範囲では、より低い活性化エネルギー（Ｅａ）を示し、好ましいことがわかった。
(Activation energy (Ea))
The activation energy Ea (kJ / mol) is calculated using the Arrhenius equation: σ = Aexp (−Ea / kT) (σ: conductivity, A: frequency factor, k: Boltzmann constant, T: absolute temperature) Obtained from the slope of the Arrhenius plot. The obtained results are shown in Tables 1 and 2. When the Ca substitution amount a (at%) was in the range of 2 or more and 10 or less, lower activation energy (Ea) was shown, and when it was 5 at% or less, a lower value was shown. Further, it was found that when the La substitution amount a (at%) is in the range of 2 or more and 10 or less, lower activation energy (Ea) is exhibited, which is preferable.
ＣａやＬａを適量添加することで、伝導度が向上し、活性化エネルギーＥａが低下する理由については、例えば、適量のＣａやＬａをＳｒと置換すると、伝導するリチウムイオン周りの構造がより好適なものとなり、リチウムイオンの移動が容易になるためであると考えられた。なお、Ｓｒと置換する元素は、Ｃａ以外の元素、例えばＢａ、Ｓｃ、Ｙ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ及びＬｎ（原子番号５７〜７１のランタノイド）などであっても、同様の構造変化が見込まれることから、同様の効果が得られるものと推察された。 The reason why the conductivity is improved and the activation energy Ea is reduced by adding an appropriate amount of Ca or La is, for example, when the appropriate amount of Ca or La is replaced with Sr, the structure around the conductive lithium ion is more preferable. It was thought that this was because the movement of lithium ions was facilitated. It should be noted that even if the element that substitutes Sr is an element other than Ca, such as Ba, Sc, Y, Na, K, Rb, Cs, and Ln (lanthanoids having an atomic number of 57 to 71), the same structural change occurs. It was speculated that similar effects could be obtained from the expected.
（活物質との反応性の検討）
ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物であるＬｉ3/8Ｓｒ7(1-a)/16Ｃａ7a/16Ｔａ3/4Ｚｒ1/4Ｏ3（ａ＝０．０３７５の実験例７，ＬＳＴＺ−Ｃａとも称する）に活物質を混合して焼結させ、その反応性を検討した。焼結温度は、４００℃〜９００℃とした。図１０は、実験例７のペロブスカイト型イオン伝導性酸化物の粉末にＬｉＮｉ0.5Ｍｎ1.5Ｏ4（ＬＮＭとも称する）の粉末を混合して焼成した試料のＸ線回折測定結果である。図１１は、実験例７のペロブスカイト型イオン伝導性酸化物の粉末にＬｉ4Ｔｉ5Ｏ12（ＬＴＯとも称する）を混合して焼成した試料のＸ線回折測定結果である。図１０、１１に示すように、ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物は、正極活物質（ＬＮＭ）や負極活物質（ＬＴＯ）と焼成しても、副相は生じず、反応性が低く化学的に安定であることがわかった。
(Examination of reactivity with active material)
Li 3/8 Sr 7 (1-a) / 16 Ca 7a / 16 Ta 3/4 Zr 1/4 O 3 (a = 0.0375 ) , which is a perovskite type ion conductive oxide in which the Sr site is substituted with Ca Experimental Example 7, also referred to as LSTZ-Ca) was mixed with an active material and sintered, and the reactivity was examined. The sintering temperature was 400 ° C to 900 ° C. FIG. 10 shows the result of X-ray diffraction measurement of a sample obtained by mixing LiNi 0.5 Mn 1.5 O 4 (also referred to as LNM) powder with the perovskite ion conductive oxide powder of Experimental Example 7 and firing it. FIG. 11 shows the result of X-ray diffraction measurement of a sample obtained by mixing Li 4 Ti 5 O 12 (also referred to as LTO) with the perovskite type ion conductive oxide powder of Experimental Example 7 and firing it. As shown in FIGS. 10 and 11, the perovskite ion conductive oxide in which the Sr site is replaced with Ca does not generate a subphase even when fired with a positive electrode active material (LNM) or a negative electrode active material (LTO). It was found that the reactivity was low and it was chemically stable.
（有機電解質との複合体の検討）
固体電解質の板状体の両面に有機電解質を積層した複合体を作製し、抵抗値（Ω）を検討した。ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物（実験例７，ＬＳＴＺ−Ｃａ）からなる固体電解質と、有機電解質としてポリエチレンオキサイド（ＰＥＯ）と、Ｌｉ金属箔とを表裏に積層した、Ｌｉ／ＰＥＯ／ＬＳＴＺ−Ｃａ／ＰＥＯ／Ｌｉを実験例１３の評価複合体とした。また、Ｌｉ0.35Ｌａ0.55ＴｉＯ3（ＬＬＴとも称する）を固体電解質とした以外は実験例１３と同様の構成とした複合体を実験例１４とした。表３に実験例１３、１４の構成及び抵抗値（Ω）をまとめた。ＬＬＴは、２５℃において伝導度が７×１０-5（Ｓ／ｃｍ）であり、電池の内部抵抗を下げるには十分でない。一方、ＬＳＴＺ−Ｃａは、２５℃において伝導度が４×１０-4（Ｓ／ｃｍ）であり、実験例１４に比して低い抵抗値を示し、電池の内部抵抗をより下げられることがわかった。
(Examination of complex with organic electrolyte)
A composite was prepared by laminating an organic electrolyte on both sides of a solid electrolyte plate, and the resistance value (Ω) was examined. Li layer in which a solid electrolyte composed of a perovskite ion conductive oxide (Experimental Example 7, LSTZ-Ca) in which Sr sites are substituted with Ca, polyethylene oxide (PEO) as an organic electrolyte, and a Li metal foil are laminated on both sides. / PEO / LSTZ-Ca / PEO / Li was used as the evaluation composite of Experimental Example 13. In addition, Experimental Example 14 was a composite having the same configuration as Experimental Example 13 except that Li 0.35 La 0.55 TiO 3 (also referred to as LLT) was used as the solid electrolyte. Table 3 summarizes the configurations and resistance values (Ω) of Experimental Examples 13 and 14. LLT has a conductivity of 7 × 10 −5 (S / cm) at 25 ° C. and is not sufficient to lower the internal resistance of the battery. On the other hand, LSTZ-Ca has a conductivity of 4 × 10 −4 (S / cm) at 25 ° C., shows a lower resistance value than that of Experimental Example 14, and can lower the internal resistance of the battery. It was.
（試験セル（半電池）の作製）
次に、全固体リチウム二次電池について試験セル（半電池）を作製し検討した。図１２は、試験セル３０の説明図である。ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物（ＬＳＴＺ−Ｃａ，実験例７）からなる固体電解質層３１のペレットを作製し、その一方の面に活物質層３３（薄膜）を形成した（複合体４０）。また、固体活物質層３１の他方の面に有機電解質層３９を介してリチウム金属の対極３６を貼り合わせた。正極活物質として、ＬｉＣｏＯ2（ＬＣＯとも称する）と、ＬＮＭとを用い、負極活物質としてＬＴＯを用いた。有機電解質層３９としてポリエチレンオキサイド（ＰＥＯ）を用いた。試験セルは、Ｌｉ／ＰＥＯ／ＬＳＴＺ−Ｃａ／ＬＣＯ半電池（実験例１５）と、Ｌｉ／ＰＥＯ／ＬＳＴＺ−Ｃａ／ＬＮＭ半電池（実験例１６）と、Ｌｉ／ＰＥＯ／ＬＳＴＺ−Ｃａ／ＬＴＯ半電池（実験例１７）とした。
(Production of test cell (half-cell))
Next, a test cell (half battery) was prepared and examined for an all solid lithium secondary battery. FIG. 12 is an explanatory diagram of the test cell 30. A pellet of the solid electrolyte layer 31 made of a perovskite ion conductive oxide (LSTZ-Ca, Experimental Example 7) in which the Sr site was replaced with Ca was produced, and an active material layer 33 (thin film) was formed on one surface thereof. (Composite 40). Further, a counter electrode 36 made of lithium metal was bonded to the other surface of the solid active material layer 31 through an organic electrolyte layer 39. LiCoO 2 (also referred to as LCO) and LNM were used as the positive electrode active material, and LTO was used as the negative electrode active material. Polyethylene oxide (PEO) was used as the organic electrolyte layer 39. The test cells were Li / PEO / LSTZ-Ca / LCO half-cell (Experimental Example 15), Li / PEO / LSTZ-Ca / LNM half-cell (Experimental Example 16), and Li / PEO / LSTZ-Ca / LTO half-cell. A battery (Experimental Example 17) was obtained.
(電池評価)
電池評価として、サイクリックボルタモグラム（ＣＶ）を測定した。ＣＶ測定は、電気化学測定システム（北斗電工社製、ＨＺ−３０００）を用いて行った。ＣＶ測定は、実験例１５では、２５℃、０．１ｍＶ／ｓｅｃ、Ｌｉ+／Ｌｉ基準で３．０Ｖ〜４．２Ｖの範囲で行った。実験例１６では、２５℃、０．１ｍＶ／ｓｅｃで、Ｌｉ+／Ｌｉ基準で３．５Ｖ〜５．０Ｖの範囲で行った。実験例１７では、２５℃、０．１ｍＶ／ｓｅｃで、Ｌｉ+／Ｌｉ基準で１．０Ｖ〜３．０Ｖの範囲で行った。図１３は、ＬＣＯ（ＬｉＣｏＯ2）試験セル（実験例１５）のサイクリックボルタモグラムである。図１４は、ＬＮＭ（ＬｉＮｉ0.5Ｍｎ1.5Ｏ4）試験セル（実験例１６）のサイクリックボルタモグラムである。図１５は、ＬＴＯ（Ｌｉ4Ｔｉ5Ｏ12）試験セル（実験例１７）のサイクリックボルタモグラムである。図１３〜１５に示すように、ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物では、全ての半電池で酸化還元電流を確認した。したがって、これらの活物質を用いて充放電ができることがわかった。特に、５Ｖ級の高電位活物質であり、固体電解質との組み合わせで充放電が困難であるＬＮＭとの組み合わせにおいて充放電できることがわかった。これらの結果より、ＳｒサイトをＣａで置換したペロブスカイト型イオン伝導性酸化物を用いて作製した全固体リチウム二次電池は、有効に充放電することができることが明らかとなった。
(Battery evaluation)
As a battery evaluation, a cyclic voltammogram (CV) was measured. CV measurement was performed using an electrochemical measurement system (HZ-3000, manufactured by Hokuto Denko). In Experimental Example 15, CV measurement was performed in a range of 3.0 V to 4.2 V on the basis of 25 ° C., 0.1 mV / sec, and Li + / Li. In Experimental Example 16, the measurement was performed at 25 ° C. and 0.1 mV / sec in the range of 3.5 V to 5.0 V on the basis of Li + / Li. In Experimental Example 17, the measurement was performed at 25 ° C. and 0.1 mV / sec in a range of 1.0 V to 3.0 V on the basis of Li + / Li. FIG. 13 is a cyclic voltammogram of an LCO (LiCoO 2 ) test cell (Experimental Example 15). FIG. 14 is a cyclic voltammogram of an LNM (LiNi 0.5 Mn 1.5 O 4 ) test cell (Experimental Example 16). FIG. 15 is a cyclic voltammogram of an LTO (Li 4 Ti 5 O 12 ) test cell (Experimental Example 17). As shown in FIGS. 13 to 15, in the perovskite type ion conductive oxide in which the Sr site was substituted with Ca, the redox current was confirmed in all the half-cells. Therefore, it was found that charging and discharging can be performed using these active materials. In particular, it has been found that charging and discharging can be performed in combination with LNM, which is a high potential active material of 5 V class and is difficult to charge and discharge in combination with a solid electrolyte. From these results, it became clear that the all-solid-state lithium secondary battery manufactured using the perovskite type ion conductive oxide in which the Sr site is replaced with Ca can be charged and discharged effectively.
なお、本発明は上述した実施例に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 In addition, this invention is not limited to the Example mentioned above at all, and as long as it belongs to the technical scope of this invention, it cannot be overemphasized that it can implement with a various aspect.
本発明は、イオン伝導性を用いる技術分野、例えば、固体電解質に利用可能である。 The present invention is applicable to a technical field using ionic conductivity, for example, a solid electrolyte.
１０，１０Ｂ 全固体型リチウム二次電池、１１ 固体電解質層、１３ 正極活物質層、１４ 集電体、１６ 負極活物質層、１７ 集電体、１８，１９ 有機電解質層、２０〜２３ 複合体、３０ 試験セル、３１ 固体電解質層、３３ 正極活物質層、３６ 対極、３９ 有機電解質層、４０，４３ 複合体。 10, 10B All-solid-state lithium secondary battery, 11 Solid electrolyte layer, 13 Positive electrode active material layer, 14 Current collector, 16 Negative electrode active material layer, 17 Current collector, 18, 19 Organic electrolyte layer, 20-23 Composite , 30 Test cell, 31 Solid electrolyte layer, 33 Positive electrode active material layer, 36 Counter electrode, 39 Organic electrolyte layer, 40, 43 Composite.
Claims (12)
Ｃａ、Ｂａ、Ｍｇ、Ｓｃ、Ｙ、Ｒｂ、Ｃｓ及びＬｎ（原子番号５７〜７１のランタノイド）のうち１種以上を含む元素Ａと、
Ｔａ、Ｎｂ、Ｗ、Ｍｏ、Ｒｅ、Ｒｕ及びＯｓのうち１種以上を含む元素Ｍと、
を含むペロブスカイト型イオン伝導性酸化物。 Li, Sr, and Zr,
An element A containing at least one of Ca, Ba, Mg, Sc, Y, Rb, Cs and Ln (lanthanoids having an atomic number of 57 to 71);
An element M containing one or more of Ta, Nb, W, Mo, Re, Ru and Os;
Perovskite ion-conducting oxide containing
活性化エネルギーＥａが４０（ｋＪ／ｍｏｌ）より小さい、請求項１〜３のいずれか１項に記載のペロブスカイト型イオン伝導性酸化物。 The electrical conductivity σ (25 ° C.) is 7.0 × 10 −5 (S / cm) or more,
The perovskite type ion conductive oxide according to any one of claims 1 to 3, wherein the activation energy Ea is smaller than 40 (kJ / mol).
前記固体電解質層に隣接しリチウムを吸蔵放出する活物質を含む活物質層と、を備えた複合体。 A solid electrolyte layer comprising the perovskite type ion conductive oxide according to any one of claims 1 to 8;
An active material layer including an active material that adsorbs and releases lithium adjacent to the solid electrolyte layer.
前記固体電解質層に隣接しリチウムイオンを伝導する有機電解質と、を備えた複合体。 A solid electrolyte layer comprising the perovskite type ion conductive oxide according to any one of claims 1 to 8;
An organic electrolyte adjacent to the solid electrolyte layer and conducting lithium ions.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015045733 | 2015-03-09 | ||
| JP2015045733 | 2015-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016169145A true JP2016169145A (en) | 2016-09-23 |
| JP6451672B2 JP6451672B2 (en) | 2019-01-16 |
Family
ID=56983044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016043447A Expired - Fee Related JP6451672B2 (en) | 2015-03-09 | 2016-03-07 | Perovskite type ion conductive oxide, composite and lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6451672B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020045274A (en) * | 2018-09-12 | 2020-03-26 | 日立金属株式会社 | Ion conductive oxide, and battery including the same, and method for producing ion conductive oxide |
| JP2020045273A (en) * | 2018-09-12 | 2020-03-26 | 日立金属株式会社 | Ion conductive oxide, and battery including the same, and method for producing ion conductive oxide |
| JP2020136123A (en) * | 2019-02-21 | 2020-08-31 | 株式会社豊田中央研究所 | Perovskite ion-conducting oxide, composite, and lithium secondary battery |
| JP2020164399A (en) * | 2019-03-27 | 2020-10-08 | 日立金属株式会社 | Ion conductive oxide and method for producing the same |
| JP2021004155A (en) * | 2019-06-27 | 2021-01-14 | 日立金属株式会社 | Method for producing ion-conductive oxide |
| WO2021039834A1 (en) | 2019-08-30 | 2021-03-04 | 昭和電工株式会社 | Lithium ion-conducting oxide |
| WO2021039835A1 (en) | 2019-08-30 | 2021-03-04 | 昭和電工株式会社 | Lithium-ion-conductive oxide |
| WO2021132582A1 (en) | 2019-12-27 | 2021-07-01 | 昭和電工株式会社 | Lithium-ion-conductive oxide sintered body and use thereof |
| WO2021132581A1 (en) | 2019-12-27 | 2021-07-01 | 昭和電工株式会社 | Lithium ion–conductive oxide and use for same |
| JP2021136223A (en) * | 2020-02-28 | 2021-09-13 | 三井金属鉱業株式会社 | Lithium ion conductor, and electrode mixture and battery including the same |
| JP2022061217A (en) * | 2020-10-06 | 2022-04-18 | トヨタ自動車株式会社 | Negative active material, method for manufacturing negative active material, and lithium ion battery |
| US11909028B2 (en) * | 2019-10-23 | 2024-02-20 | Samsung Electronics Co., Ltd. | Cathode for metal-air battery, preparing method thereof, and metal-air battery comprising the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11955597B2 (en) | 2019-12-02 | 2024-04-09 | Samsung Electronics Co., Ltd. | Solid electrolyte, preparation method thereof, metal air battery including the same, and electrochemical device including the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006500311A (en) * | 2002-09-24 | 2006-01-05 | コーニング・インコーポレーテッド | Electrolyte perovskite |
| JP2013032259A (en) * | 2011-06-29 | 2013-02-14 | Toyota Central R&D Labs Inc | Garnet type ionic conductivity oxide and manufacturing method of the same |
-
2016
- 2016-03-07 JP JP2016043447A patent/JP6451672B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006500311A (en) * | 2002-09-24 | 2006-01-05 | コーニング・インコーポレーテッド | Electrolyte perovskite |
| JP2013032259A (en) * | 2011-06-29 | 2013-02-14 | Toyota Central R&D Labs Inc | Garnet type ionic conductivity oxide and manufacturing method of the same |
Non-Patent Citations (1)
| Title |
|---|
| SOLID STATE IONICS, vol. 167, JPN6018021909, 2004, pages 263 - 272, ISSN: 0003815665 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020045273A (en) * | 2018-09-12 | 2020-03-26 | 日立金属株式会社 | Ion conductive oxide, and battery including the same, and method for producing ion conductive oxide |
| JP2020045274A (en) * | 2018-09-12 | 2020-03-26 | 日立金属株式会社 | Ion conductive oxide, and battery including the same, and method for producing ion conductive oxide |
| JP7267154B2 (en) | 2018-09-12 | 2023-05-01 | 三井金属鉱業株式会社 | Ion-conducting oxide, battery using the same, and method for producing ion-conducting oxide |
| JP7267155B2 (en) | 2018-09-12 | 2023-05-01 | 三井金属鉱業株式会社 | Ion-conducting oxide, battery using the same, and method for producing ion-conducting oxide |
| JP2020136123A (en) * | 2019-02-21 | 2020-08-31 | 株式会社豊田中央研究所 | Perovskite ion-conducting oxide, composite, and lithium secondary battery |
| JP7281296B2 (en) | 2019-02-21 | 2023-05-25 | 株式会社豊田中央研究所 | Perovskite-type ion-conducting oxides, composites and lithium secondary batteries |
| JP7267156B2 (en) | 2019-03-27 | 2023-05-01 | 三井金属鉱業株式会社 | Ion-conducting oxide and method for producing the same |
| JP2020164399A (en) * | 2019-03-27 | 2020-10-08 | 日立金属株式会社 | Ion conductive oxide and method for producing the same |
| JP2021004155A (en) * | 2019-06-27 | 2021-01-14 | 日立金属株式会社 | Method for producing ion-conductive oxide |
| JP7319844B2 (en) | 2019-06-27 | 2023-08-02 | 三井金属鉱業株式会社 | Ion-conducting oxide and method for producing the same |
| WO2021039835A1 (en) | 2019-08-30 | 2021-03-04 | 昭和電工株式会社 | Lithium-ion-conductive oxide |
| KR20220028114A (en) | 2019-08-30 | 2022-03-08 | 쇼와 덴코 가부시키가이샤 | Lithium Ion Conductive Oxide |
| WO2021039834A1 (en) | 2019-08-30 | 2021-03-04 | 昭和電工株式会社 | Lithium ion-conducting oxide |
| KR20220032583A (en) | 2019-08-30 | 2022-03-15 | 쇼와 덴코 가부시키가이샤 | Lithium Ion Conductive Oxide |
| US11909028B2 (en) * | 2019-10-23 | 2024-02-20 | Samsung Electronics Co., Ltd. | Cathode for metal-air battery, preparing method thereof, and metal-air battery comprising the same |
| KR20220122604A (en) | 2019-12-27 | 2022-09-02 | 쇼와 덴코 가부시키가이샤 | Lithium ion conductive oxide and uses thereof |
| EP4082971A1 (en) | 2019-12-27 | 2022-11-02 | Showa Denko K.K. | Lithium-ion-conductive oxide sintered body and use thereof |
| WO2021132581A1 (en) | 2019-12-27 | 2021-07-01 | 昭和電工株式会社 | Lithium ion–conductive oxide and use for same |
| WO2021132582A1 (en) | 2019-12-27 | 2021-07-01 | 昭和電工株式会社 | Lithium-ion-conductive oxide sintered body and use thereof |
| KR20220122603A (en) | 2019-12-27 | 2022-09-02 | 쇼와 덴코 가부시키가이샤 | Lithium ion conductive oxide sintered compact and uses thereof |
| JP2021136223A (en) * | 2020-02-28 | 2021-09-13 | 三井金属鉱業株式会社 | Lithium ion conductor, and electrode mixture and battery including the same |
| JP7349935B2 (en) | 2020-02-28 | 2023-09-25 | 三井金属鉱業株式会社 | Lithium ion conductor, electrode mixture and battery containing the same |
| JP2022061217A (en) * | 2020-10-06 | 2022-04-18 | トヨタ自動車株式会社 | Negative active material, method for manufacturing negative active material, and lithium ion battery |
| JP7435394B2 (en) | 2020-10-06 | 2024-02-21 | トヨタ自動車株式会社 | Negative electrode active material, method for producing negative electrode active material, and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6451672B2 (en) | 2019-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6451672B2 (en) | Perovskite type ion conductive oxide, composite and lithium secondary battery | |
| US20200411850A1 (en) | Battery | |
| KR101234965B1 (en) | Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery including the same | |
| US9960418B2 (en) | Cathode active material, preparation method thereof, and lithium secondary battery comprising the same | |
| JP5381640B2 (en) | Lithium secondary battery | |
| JP5115891B2 (en) | Non-aqueous secondary battery comprising a positive electrode active material and a positive electrode including the same | |
| JP5471527B2 (en) | Lithium secondary battery and electrode for lithium secondary battery | |
| CN112154565A (en) | Composite particle, method for producing composite particle, electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| US20150155554A1 (en) | Active material of lithium ion secondary battery and lithium ion secondary battery using the same | |
| JPWO2019135342A1 (en) | Solid electrolyte material and battery | |
| JP2018056114A (en) | Cathode active material for battery, and battery | |
| Ette et al. | Mo3Nb2O14: A high-rate intercalation electrode material for Li-ion batteries with liquid and garnet based hybrid solid electrolytes | |
| JP2017152369A (en) | Positive electrode active material and battery | |
| US20230307702A1 (en) | Solid-state electrolyte, solid-state battery including the electrolyte, and method of making the same | |
| JP5644083B2 (en) | Negative electrode active material for lithium secondary battery, lithium secondary battery using the same, and method for producing negative electrode active material for lithium secondary battery | |
| JPWO2020110479A1 (en) | Negative electrode material and battery | |
| JP2012089441A (en) | Positive electrode active material, and nonaqueous secondary battery with positive electrode containing the same | |
| JP5417978B2 (en) | Negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP2018008843A (en) | Solid electrolyte, all-solid battery and manufacturing method thereof | |
| JP5147951B2 (en) | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using the same | |
| JP2021082420A (en) | Negative electrode active material, negative electrode and battery cell | |
| JP2020077571A (en) | Composite structure, lithium battery, and method for manufacturing composite structure | |
| WO2010146776A1 (en) | Negative electrode active material for lithium ion secondary battery, and lithium ion secondary battery using same | |
| JP7193315B2 (en) | Lithium-manganese composite oxide, lithium secondary battery, and method for producing lithium-manganese composite oxide | |
| JP2012038508A (en) | Positive electrode active material and nonaqueous secondary battery with positive electrode containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171017 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180612 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180614 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180802 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181113 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181126 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6451672 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |