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`EP 3 428 929 A‘1
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`{12}
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`EUROPEAN PATENT APPLICATION
`published in accordance with Ar. 153(4) EPC
`
`{43} Date of publication:
`16.01.2019 Bulletin 2019/03
`
`(21) Application number. 17763262.7
`
`(22) Date offiling: 07.03.2047
`
`{64} Int oh:
`HOT F108 COR
`HOTB 73fog R880
`HOTM 1010585 (200-08)
`
`HOT Fag @eceed
`HOTM 7OIGSEZ OTRO
`
`{86} International applination number:
`PCTHIP2017/069058
`
`i87} International publication number.
`WO 2047/154922 (14.09.2017 Gazetie 2047/37}
`
`{84} Designated Contracting States:
`AL AT BE BG CH CY C2 DE DK EE ES FIFR GB
`GR HR HUTEISIT LILT LU LY MC MK MT NL NO
`PL PT RO RS SE SISK SM TR
`Designated Extension States:
`BA ME
`Designated Validation States:
`MA MB
`
`(30) Priority: 08.03.2046 JP 2076044362
`
`i741) Applicant Murata Manufacturing Co., Ltd.
`Nagaokakyo-shi, Kyoto 617-8558 (JP}
`
`invertors:
`&72)
`* YOSHIOKA Makato
`
`*
`
`ITO Akisuke
`Nagaokakyo-shi
`Kyoto 617-8585 CIP}
`* TAKANO Rychei
`Nagackakyo-shi
`Kyote 617-8585 {JP}
`ISHIKURA Takeo
`Naqaokakyo-shi
`Kyoto 617-8555 (IP)
`
`+
`
`{74} Representative: Reeve, Nicholas Edward
`Raddie & Grosa LLP
`The White Chapel Guilding
`40 Whitechapel High Street
`Londen E1 808 {6B}
`
`Nagaokakyo-shi
`Kyoto 647-3545 {JP}
`
`(545
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`SOLID ELECTROLYTE, ALL-SOLID BATTERY, SOLID ELECTROLYTE MANUFACTURING
`METHOD AND ALL-SOLID BATTERY MANUFACTURING METHOD
`
`The tonic conductivity af a solid electrolyte layer is improved, and the battery characteristics of an all solid state
`{57}
`battery are improved.
`The solid electrolyie has a NaSlCON-type crystal structure. The solid electrolyie is representedby a general formula
`Lig,,efanMiPO,), (Limay be partially substituted with at least one selected from the group consisting of Na, K, Rb,
`Os, Ag, and Ca. P may be partially subsiltuted with al least one of B and Si, and M contains alfeast one element capable
`of stabilizing or partially stabilizing the tetragonal or cubic crystal structure of a high-temperature phase of ZrO., and
`250 <a 42.00, 0.04 <b< 1.90, and G.0t <0 < 1.90).
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`EP3428929A‘
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`Printed hy Jouve, 7SRARIS (ERG
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`(Cont. next page)
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`E P 3 428 929 Ai
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`Description
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`TECHNICAL FIELD
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`EP 3 428 929 At
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`fO001} Thepresent invention retales to a solid electrolyie, an all solid stale battery, @ method for producing a solic
`sleciralyte, and a methad for producing an all salid statebattery.
`
`BACKGROUND ART
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`fO0G2] Conventionally, all solid state batteries are known as seoandary batteries which are excellent in reliability and
`safety. For axample, Patent Document 1 discloses an all solid state ballery thal has an electrolyte film somposed ofa
`NaSiCon-type fie. In addition, Patent Document 2 discloses a lithium ion conductive solid slectrolyle represented by
`the chemical formula Li,..M2fs_,(PO.), din the formula, M represents at least one element selectedfrom Al and rare-
`earth alernants, and x represents 0.4 to 1.9).
`
`PRIOR ART DOCUMENTS
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`PATENT DOCUMENTS
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`[o003]
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`Patent Document 1: Published Japanese Transistion of PCT International Applicatian No. 2G12-870987
`Patent Docurnent 2: Japanese Patent Application Laid-Open No. 2-250264
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`SUMMARY OF THE INVENTION
`
`Protiem tp be solved by the invention
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`in all solid slate batteries, there is a demand for improving the tonic conductivity of solid electrolyte layers and
`[5004]
`improving ihe battery characteristics of the all solid state batiaries,
`f0005]
`A main object of the present invention is to improve the fonia conductvily of a solid alectrolvie layer, areal improve
`the battery characteristics of an all solid state battery.
`
`Means for salving the problem
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`[D008] Asolid etectrolvie according to ihe present invention has a NaS!CON-type crystal structure. The salid electrolyte
`according tp the present inveniion is represeniad by a general formula Li,,,2rs,Md{POg), (Li may be partially substiluted
`with af least one selected from the group consisting of Na, K, Rb, Cs, Aq. and Ca, P may be partially substituted with al
`least one of B and Si, and M contains at least one element capable of stabilizingor partially stabilizing the tetragonal or
`cubic crystal structure of a high-temperature phase of £35, and -0.90 4 4 < 2.00, 0.0) s bs 1.90, and 0.01 se < 1.90},
`fH007] The solid alectrobyte according to the present hivention is a solid electralyte that has a NaSiCON-lyoe crystal
`structure, represented by the general formula Li, ,.2f,.M (PO), (Li may be partially substihided with alleast oneselected
`from the group consisting of Na, K, Rb, Os, Ag, and Ca, P may be partially substituted with at feast one of B and Si. and
`M contains al least one element capable of stabilizing or partially stabilizingthe tetragonal or cubic crystal structure of
`a high-lempenature phase of ZrO», and -.90 sa < 2.00, 0.01 <6 < 1.90, and 0.01 s¢ < 1.90). Therefore, the use of the
`solid electrolyte according fo the present invention can achieve a solid elestralyte layer which has a high lan corluotivily.
`Accordingly, an all solid state battery can be achieved which has excellent battery characteristics.
`fFOOOS]
`In the solid electrolyte according te the present invention, the M preferably contains at least ane selected from
`ihe group corisisting of ¥, Ca, Mg. Sc, and janthanoid elements, as ihe at least one elermant capableof stabihzing or
`partially stebilzing the tetragonal or cubic crystal structure of the high-temperature phase of ZrO.
`[e008]
`In the solid electrolyte according to the present invention, the M preferably contains al jeast one selected from
`the group consisting of Y, Ca, and Mg, as the af least one element capable of stabilizing or partially stabilizing the
`telragonal or oubic crystal structure of the figh-lemperature phase of 2rO,.
`fFooiG]
`In the solid electraiyte according to the present invention, ¢ preferably meets O.01 =< c <= 0.38 in the general
`formula.
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`formula.
`fOIN2]
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`in the soli clectrolyie according ta the present invention, c oreferably meets 0.02 = 6 =: 0.20 in the general
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`In the solid electrolyte according to the present invention, M preferably further contains at least one element
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`selected frorn the grauip consisting of Al, Ga, Sc, In, Ge, Ti, Ru, Sn, Hf Ce, V. Nb, Ta, BL and W.
`[8013] The solid electrolyte according fo the present Invention is preferably a solid electrolyte represented by the
`general forrmnufe Li, jodyM1. 4Me. p(PO.), ULI may be partially substituled with at feast one sefected from the group
`consisting of Na, K, Rb, Gs, Aq, and Ga, P may be partially subsituted with at least one of B and Si, Mt represents at
`least one element capable of stabilizing or partially stabilizing the telragonal or cubic crystal structure of the fhigh-
`temperature phase of ZrO., M2 represents at least one element selected jrom the group consisting of Al, Ga, Se, in,
`Ge, Ti, Ru, Sn, Hf, Ce, V, Nb, Ta, Bi and Wand -0. 80<a5 2.00, 0.0} s05 1.90, 041 s ct £0.90, and 6.01 £ o2 < 1.88}.
`fO014] Analisalid state battery according to the present Invention inclucies a solid electrolyte layer, a positive electrade,
`and a negative electrode. The solid electrolyte layer includes the solid electrolyte according to the present invention.
`The pasitive electrode is joined by sintering to one surface af the salid electrolyte layer. The negative electrade is joined
`by sintering to the other surface of the solid electroiie layer.
`fads]
`Ina method for producing a solid electrolyte according to the present invention, a solid electrolyte is synthesized
`by using stabilized or partially stabilized zirconia. Synthesizing a solid electrolyte by using the partiallystabilized zirconia
`can produce a salid olectrolyte capable of forming a solidi electrolyte layer with @ high ion conductivity.
`fO046]
`Inthe method for producing 4 solid electrolyte according to the present invention, the solidelectrolyte is preferably
`synthesized by using partially stabilized zircania partlally stabiNzed with at least one element selected fram the graup
`consisting of ¥Y, Oa, Mg, Sc and a lanthanoid elemant.
`fOG77]
`Inthe method for praducing asolid electrolyte according io the present invention, the satid etectrolyte is preferably
`synthesized by using stabilized zirconia stahilized with, or partially stabilized zirconia partially stabilized with at least one
`aiement selected fram the group consisting of Y, Ca, and Mag.
`fO078]
`In a method for prealucing ar all solid state batlery according lo the present invention, an all solid state batlery
`is obtained byjoining a solid electrolyte layer including the salid electrolyie orecuiced by using the method for producing
`& solid electrolyte according to the present invention, and an electrode by sintering.
`
`Advantageous offect of the invention
`
`fO0719] According to Ihe present invention, fis possible to improve the ianic conductivity of the solid ehectrolyte layer,
`and imprave the battery characteristics of the all solid state battery.
`
`BRIEF EXPLANATION OF DRAWINGS
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`FIG. 1 is a schematic cross-sectional view of an all solid state bailery according fp one embudirnent of the present
`invention,
`FIG, 2 is an ¥-ray diffraction chart for sold electrolyte layers prepared according to sach of Examples 1 to 6 and
`Comparative Example 1.
`Fits. J is a cole-cole plot af the solid alectralyte preparad according to Example 1.
`FIG. 4 is 4 cole-cole plot of the solid electrolyte prepared according to Comparative Example 1.
`FIG. § is an X-ray diffraction chart for the solid electrolytelayers prepared according to each of Examples 9 to 15.
`
`MOOE FOR CARRYING OUT THE INVENTION
`
`foo21] Anexamople ofa preferred embodiment of the present Invention wil be described below. However, thefollowing
`embodimentis considered by way of exaripie anly. The present inverticn is not lirdited to the following embodimern in
`any wey.
`In addition, members that have substantially the same functions shall be denoted by the sane reference symbols
`fX227
`in the respective drawings referred to in the embodiment and the like, in addition, tha drawings referenced in the em-
`bodiment and ihe like are schematically made. The raline belvean the dimensions of objects drawn in the drawings,
`and the Eke may,
`in some cases, differ from the ratios between the dimensions of actual objects, or the ke. The
`dirnensionalratios of objects, and the like ray differ behveen the drawings as weillin some cases. The specific dimensional
`ratios of objects, and the like should be determined in view of the following description.
`fO023} FG. 4 is a schematic cross-sectional view of an all solid state battery 1 according fo ihe preset embodiment.
`As shown in FRS. 1, the battery inchides a negative electrode 12, a positive electrode 11, and a solid electrolyte layer 13.
`fO024] The postive electrode 11 inchides positive electrode active material particies. Examples of the positive electrode
`active material particles prefenably used include iithturm-coantaining ohosphate compoundparticles which have a NASI-
`CON-iype structure, [Nhtum-containing phosphate compound particles which have an olivine-type structure, [ithium-
`containing layered oxide particles, thium-containing oxide particles which have a spinel-type structure. Specific examples
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`EP 3 428 929 Ai
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`of the preferably used Hthium-containing phosphate compound which has a NASICON-typestructure include LigVo(POs},.
`Specific examples of the preferably used ithiumt-containing phosphate cormpound which has an oflvine-type structure
`include LiFePO, and LivinPO,. Specific examples of the preferably used Ithivim-containing layered oxide particias
`include LICeO. and LICD, .NiynMn,.,O.. Specific examples of the preferably used Hihium-containing oxide which has
`a spinel-lype structure include LIMn,O, and LIN,«Mn, .O,. Only one of these positive electrode active material particles
`may be used, ar twa ar more thereof may be used in mixture.
`fO025] The positive electrode 17 may further include a solid electrafyte. The type of salid electrolyte included in the
`positive electrode 774
`is not particularly limited, but it is preferable ta Inchide the same type of solid electratyie as the
`solid electrolyte included in the solid electrolyte layer 13.
`fOO26] The negalive electrode 12 inchides negative clectrode active rnaterial parlicies. Specific exarnples of the neg-
`alive electrode active material particles preferably used include compound particles represented by MO, (MIs al least
`one selected fram the group consisting of Ti, Si, Sn, Cr, Fe, Nb and Alo. 0.9 4% < 2.5), graphite-lithiumn sompound
`particles, lithium alley particies, ithhum-containing phosphate compound particles which have a NASICON-type structure,
`hithitum-sontaining phosphate compound particles which have an olivine-type structure, and [Nhium-cortaining oxide
`particles which have a spinel-type structure. Specific examples of the lithium alloy preferably used include LAIalloys.
`Specific exanmmpies of the preferably used |thlunt-containing phosphate compound which hes an olivine-type structure
`include Li, Fe.(PO,},. Specific examples of the preferably used Hthium-containing oxide which has a spinel-type structure
`include LI,TI,Q 5. Gniy one of these negative electrode active material particles may be used, or hwo or more thereaf
`may be used in mixture.
`fo027] The negative electrode 12 may further include a solid electrolyte. The type of solid electrolyte included inthe
`negative electrode 12 is not particularly limited, bul tis preferable fo inclide the same type of salid eleotralyte as ihe
`solid electrolyte included in the solid electrolyte layer 13.
`fOOG28] A aolid electrolyte layer 13is disposed between the positive electrode 17 and ihe negative electrode 12. More
`specifically, the positive electrode 11 is disposed on one side of the solid electrolyte layer 13, and the negative electrode
`12 is disposed on the other side. Each of ihe positive electrode 11 and the negative elactrode 12 is bonded by sintering
`to the solid electrolyte layer 13. More specifically, the positive electrode 11, the solid atectrolyie hayer 13, and the negative
`mlectrate 12 constitute an integrallysintered body.
`fOO29] The solic ciectrolyie isyer 13 has a NwaShCON-type crystal structure. The solid electrolyte bayer 13 includes a
`solid electrolyte represented by a general formula Li...2ro .MM(POg}y (Li may be parially substituted with al least ore
`selected from the group consisting af Na. K, Rb, Cs, Ag, and Ca, P may be partially subatituied with at least one of B
`ard Si, and M contains af least one element capable of stabilizing or partially stabilizing the tetragonal or cuble crysial
`structure of ihe high-temperature phase of ZrO, and -0.50 = a< 2.00, 0.04 <b s 1.90. and 6.01 sc = 1.96). Therefore,
`the solid electrolyte layer 135 has high ion conductivity. Accordingly, the all solid state battery | with the solid electrolyte
`layer 13 has exceiient battery characteristics such as a pawer density. The reasan therefor is nat known exactly, but
`believed lo be because the addition of M makes a high ionic conduction phase more likely io be formed in the solid
`electrolyte. However, the excessively high content of M In the solid electrolyte is believed to produce M that falls to serve
`as a solid solution in ihe NaSICON-iypesolid electratyte, thereby causing the M fo form a different phase, and thus
`decreasing the jon canduclivity. Accordingly, in the ganeral formula mentioned above, o prafarably meets 0.07 = ¢ =
`0.38, more preferably 0.02 <0 <4 0.20.
`[9030]
`Specific examples of preferabie M include, for example, lanthanoid elernents such as Y. Ca, Mg, Sc, and Ce.
`Above all, from the viewpoint of actieaving a higher ionic conductivity, Mots preferably af beast one selected from ire
`group consisting af Y, Ca, Ma, Sc, and lanthanoid elements. The reasan why = highionic conductivity can be achieved
`by using ¥Y. Ca. or Mg as M is not known exactly, bul believed to be because a high ionic conduction phase is made
`more likely to be formed and maintained.
`fO034] M in the general formula mentioned above preferably further contains another element for maintaining the
`NaSiCon-tyoe orvstal structure evan in the case of substitution with Zr of the general formula. Spectfically, M in the
`general formula preferably further contains at least one element selected frarn ihe group cansisiing of Al, Ga, Sc, tn,
`Ge, Tl Ru, Sn, Hf Ce, V. Nb, Ta, BL and W. This is because, in this case, the lonic conductivity of the solid electrolyte
`oan be futher rioreasecd. The reasan therefor is not known a@xacily, but believed in be becausa the high tonic canduckon
`phase is made much more likely ta be formed.
`[O32] Snectically, the solid electroiyie according to the present invention is preferably a solid electrofyte represented
`by the general formula Liv.ffMi. Meo (PO,g}, (Li may be partially substituted with at least ane selected fram the
`group consisting of Na, K, Rib, Cs, Aq, and Ca, P may be partially substitufed with al least one of B arc Si, Mi represents
`at least one element capable of stabilizing or partially stabilizing the tetragonal or cubic crystal structureof the high-
`lamperature phase of 2rO., M2 represenis at least one element selacted from the group consisting of Al, Ga, Sc, In,
`Se, Ti, Ru. Sa, Hf, Ce, V, Nb, Tia, Bi, and VY, and -0.50 < a< 2.00, 0.0) sb s 1.90, 0.07 sc¢1 40.90, and O.Ots ces
`1.89). From the viewpoint of forming a NaSlOON-type crystal stricture, cl preferably meets 0.04 2 ct = 0.90, and more
`preferably 0.01 < ct < 0.60. Likewise, from the viewpoint of forming a NaShcON-type orystal structure, c2 preferably
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`EP 3 428 929 Ai
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`meets 0.01 sce = 1.89, and more preferably 0.01 4 c2 5 1,79.
`[0033]
`In the general formula, Li may be partially substituted with at least one selected from the group consisting of
`Na, K, Rb, Cs, Ag, and Ca. in thal cease, the mohar nate of af laast ane selected frorn the graup consisting of Na, K, RE,
`ts, Ag, and Ca to LI i(Liy(at feast one selected fram the group consisting of Na, K, Rh, Cs, Ag, and Galis preferably 1
`or more ancl 289 or fess, and more preferably 5 or more and 150 or less.
`fG024]
`In the general formufa, P may be partially substituted with at least ane of B and Si. in that case, the molar ratio
`of at least one of B and Sila P (fat least one of B and SH(P) is preferably 0.0 ar more and 2.0 or Jess, and more
`preferably 0.0 or more and 6.5 or fess.
`[0035}
`Fram the viewpotnt of achieving a higher fonic conductivity. « preferably mecia -0.15 = a < 0.70. and more
`preferably -0.10 < a < 0.50. b preferably meets 0.01 <b 2 7.60. ene more preferably 0.04 <b < 1.00.
`fO036] The compound represented by the aeneral formula has 12 oxygen atoms, bad the number of oxygen alams
`included in ihe compound represented by the general formula does not have to be strictly 12 from the viewpoint of
`maintaining the neutrality between positive charge and negalive charge. In the prasant invention, the compound repre-
`sented by the general formula Li ..@fo.,MuMB. (POg), is considered to include compounds coniaining 7 mol or more
`and 15 mol or less of oxygen.
`
`{Method for Producing Solid Electroiyies
`
`f0037] Next, an example of a method far producing a solid electrolyte will be described.
`[0038]
`First. a raw material as a Li souros, a raw material as a Zr source, a raw material as a M source. and a raw
`material as a P source are weighed In desired croportians, and mixed. The oblained mixed sowsler is subjected to
`calcination, thereby preparing a calcined bedy. The obtained calcined body is subjected io fring, thereby making i
`possible to obtain a solid electralyte, Accarding to the present ermbociment, as the Zr source. partially stabilized zirconia
`is used which is partially stabilized by an element contained in M, capable of stabilizing or partially stabilizing the tetragana}
`ar ouble crystal structure of the hightemperature phase of ZrO.. For this reason, a solid electrolyte can be produced
`which has a high jon conductivify. The reason therefor is not known exactly, but believed to be because the use of, as
`the Zr source, @ zirconiurn oxie containing in advance an alernant capable of stabilizing or partially stabilizing the
`tetragonal or cubic crystal structure of the high-temperature phase of ZrO. rnakes a diferent phase untikely to he
`generated, thereby making a high tonic conduction phase likely to be formed,
`fOG39} The content of the element capable of stabilizing or partially stabilizing the tetragonal or cubic crystal structure
`of the high-lemperature phase of ZrO. in ihe partially stabilized zirconia for use as ihe Zr source is, with respect to the
`content of Zr, preferably 0.04 mols or more and 20.0 molto or less, more preferably 0.16 moor mare and 15.0 molt
`or less, and stil mare preferably 7.00 mol%or more and 10.0 mol% or less.
`
`(Method for Producing All Solid Stale Batlery T}
`
`pobaol Next an examole of a method fer producing ine al solid sinte battery 1 wilh be describect
`f0041]
`Fire! a peste is prepared by aporopiatealy mixing the aotive material parlicies and Ihe salid alectrolyie with. a
`solvent, a.resin, and the like. The paste is applied ome a sheet, and dried to form a first qrean sheet for constituting the
`positive electrode 11. Likewise, @ second green sheet for constituting the negative alectrade 12 is formed.
`f0042] A paste is prepared by appropdately mbdng the solid elactrolyte with a solvent, a resin, and the like. The pasta
`is applied and dried to prepare a third green sheet far constiiiding the solid electrolyte layer 13.
`f0043] Next, the first to third graen sheets are appropriately stacked to prepare a stacked body. The prepared stacked
`body may be pressed. Preferred pressing methods include isostatic press.
`[0044] Thereafter, the stacked body is subjected to sintering, thereby making i possible to abfain the all salid state
`battery 4.
`f9045] Hereinafter, the present invention will be desorbed in more detail, based an specific examples, but the present
`invention is not te be consiiered limited to the following examples in any way, and can be worked with changes appre-
`priately made withoul changing the scape afthe iivention.
`
`iComparative Example 1 and Examples 4 to 25)
`
`Solid electrolytes represented by the general forma Li,freM7 «M2(PO)4{Li may be partially substituted
`[9046]
`with at least one selected from the group consisting of Na. K, Rb. Cs, Aq, and Ca, P may be partially substituted with at
`least one af B and 5i, M1 represents at leasf one element capable of stabilizing or partially sbabilizing the tetragonal or
`cubic crystal structure af the high-temperature phase af ZrO., Mz represents at lsast one elernent selected from the
`group consisting of Al, Ga, Se, in, Ge, Ti, Ru, Sn, Hf, Ce, V, Nb, Ta, Bi and W. and -0.50 <a < 2.00, 8.01 2b < 1.90,
`O04 = ct s 0.90, and 0.01 < c2 = 1.69) were synthesized by the production method described in the embodiment
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`mentioned above.
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`gClomparative Example 1}
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`[0047] Raw materiais including ithium carbonate (Li,CO,}. girnoniunt oxide (2rO.}, and arnmenium dihydrogen phos-
`phate (NH,H.PO,) were weighed so as to have the composition shawn in Table 1 below. Next, the weighed raw material
`powder was encapsulated in a 5060 mi polyethylene pal made of polyelhylene, and rotated af }50 rpm for. 76 hours an
`a@ pot rack to mix the raw materiais. Next, the raw materials were subjected to firing under an air atmosphere al 500°C
`for 1 hour and at 800°C for 6 hours to remove volatile components. Next, the fired product obtained was encapsulated
`in @ BOG mi polyethylene pot maxte af polyethylene tagether with water and q 5 mm cobblestones, and subjected ta
`grinding by ralation at 150 rom for 16 hours on a pot rack. Thereafter, the product was placed on a hot plate al 120°C,
`and heeled to remiave moisture. The obtained pulverized material was sublected fo firing under an air atmosphere at
`900°C ta 200°C for 20 hours to obtain a powder of a solid electrolyte of the composition according to Camparative
`Example 7 as fisted in Table 1,
`
`(Example 1)
`
`In the same way as in Comparative Example 1 exceptihal raw materials including Whhum narbonale (LinCO4)},
`fNG48]
`Zirconium Gxide (2r3.), ammonium dihydrogen phosphate (NH,HPO), and vitriur oxide (Y.0,) were weighed as raw
`materiais so as fo have the carmposition shown in Table 7 below, a powder of a solid electrolyte was obtained,
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`(Example 2}
`
`in the same way as in Cornparative Example 1 except that raw materials inckaling Nthium carbonate (LigCO,),
`[8949]
`zirconium oxide @2rO.>), ammonium dihydrogen phosphate (NHHPO), and caichim oxide (CaQ} were weighed as raw
`materiais so as fo Nave the camposition shown in Table 1 below, a powder of a solid electrolyte was obtained.
`
`(example 3)
`
`in the same way as in Cormparative Example 1 except ihat raw materials Inchiding Nthium carbonate (LigCC.),
`[0950]
`zirconium oxide (27r.}, ammonium dihydrogen phosphate (NHZHoPO,), and magnesium oxide (MgO) were weighed
`a8 faw materiais so as to have the composition shown in Table 1 below, a powder of a solid electrohte was obtained.
`
`{Example 4)
`
`[in the same way as in Cornparative Example 1 except that raw materials inchiding lithturn carbonate (LI,CO4},
`fO051]
`Zirconium oxide (2rO.)}, ammonium dihydrogen phosphate (NHyHoPO,}, and scandium oxide (Sc,0.) were weighed as
`raw ratarials so as to have the cormmeosilian shownin Table 1 below, a powder of a solid alectralyte was. abtained.,
`
`(exaniple $)
`
`[In the same way as in Comparative Example 1 except thal raw materials inchiding lithiom carbonate (LisCOs},
`[8052]
`Zirconium oxide (2rO.), armmanium dihydrogen phosphate (NHHoPO,), and cerium oxkle (CeO) were weighed as raw
`materials so as te have the composition shown in Table 7 below. a powder of a solid electrolyte was obisined.
`
`fExample &}
`
`In the same way as in Comparative Example 7 except that without using Zirconium oxide (2nO5)}, raw materials
`{O053]
`including yilium-siahilized zirconia (Yeosefs aaOy gz}, fithium carbonate (Li.CO,) and ammonium dihydrogen phosphate
`(NH,HSPO.) were weighed as raw materials so asta have the composition shown in Table { below. a powder of 4 solid
`electrolyte was obtained.
`
`tExampie 7}
`
`In the same way as in Comparative Example 7 except that without using zirconium oxide (2rO>}, raw materials
`[0054]
`inchiding calcium stabilized zirconia (Cay oe€@Fy ayOy4 gq), hilum carbonate (Li,.CO,), and ammonium dihydmgen phos-
`phate (NHHPO) were weighed as raw materais so as to have the composition shown in Table 1 below, a powder of
`a sold electrolyte was obtained.
`
`ts&
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`+sat
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`onon
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`{Example 8)
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`ts&
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`In the same wey as in Comparative Example 1 excemt thal wifhoul using zirconium oxide (ZrO 4}, taw materials
`fO0S5]
`including magnesium stabilized zirconia (Mga ce€fy as go}, Hihium carbonate (LiCO,}, and ammonium dihydrogen
`phosphate (NH,H.PO,) were weighed as raw materais so as ic have the composition shown in Table 1 below, a powder
`of a salid electrojyte was abtained.
`
`{Example 9}
`
`[0056] Yttrlum-stabilizedzirconia with a molarratio af Zr: Y= 1.99 .0.01 was synthesized using zirconium oxide (2°04)
`and yitriuint oxide (8O.) as raw materials. In the same way as In Cornperative Example 1 except thal raw materials
`including the yiirkum stabilized zirconia and Hthiurm carbonate (LinCG.), and ammonium dihydrogen phosphate
`{NH,H.PO,) were weighed so as to have the composition shown in Table 1 below, a powder of 4 solid electrolyte was
`obtained.
`
`{Exampie 10)
`
`f8OS7] Yttriar-stabilized zirconia with a molarratio of Zr: Y= 7.98 . 0.02 was synthesized using zirconium oxide (2135)
`and yitrum oxide 4,0.) as raw materials. in the same way as in Comparative Example 1 except that raw materiais
`including the jdirlum= stebilized zirconia and lithium carbonate (Li,COs,), and ammonium dihydrogen phosphate
`(NHAHoPO.,) were weighed so as ia have the composition shown int Table 1 below, a powder of a solid electrolyle was
`abtained.
`
`(Example 14}
`
`fO0S8] Vitriurn-stabilized zirconia with a molar ratio of Zr: Y= 1.80 0.10 was synthesized using zirconium oxide (4905)
`and yitrium oxide (yY,O.) as faav materials. In ihe same way as in Gomparative Exaniple 1 except hat raw materials
`including the ytiriurn stabilized zirconia and ithium carbonate (LiIpCO.,), and ammoniurn dinydrogen phosphate
`{NHHPO.) were weighed so as to have the composition shown irt Table 7 below, a powder of a solid electrolyte was
`obtained.
`
`fExample 12}
`
` Ytirhim-stabiized zirconia wilh a molar ratia of Zr Y= 1.80 : 0.20 was synihesized using zirconiumonide (25)
`fO05O]
`and ylinurm oxide (Y¥,O,) as raw materials. In ihe same way as in Comparalive Example 1 except thal raw materials
`including the yttrium stabilized zirconia and Whim carbonate (LI,CO,), and amrnonium dihydrogen phosphate
`iNH,HPO.) were weighed so as to have the composition shown in Table 1 below, a powder of a solki electrolyte was
`obtained.
`
`th&xample 13)
`
`[8060] Ytisum-stabiized zirconia with a molar ratie of Zr -¥ = 1.78 (OG. 22was synihesized using zirconium oxide(ZrO)
`and ylirlum oxide (¥.O.) as raw materials. in the same way as in Comparative Example 1 except thal raw materials
`including the yiiunt stabilized zirconia and ithtum carbonate (LigCO }. and armonium dihydrogen phosphate
`iNHAH.PO,s) were weighed 50 as to have ihe compasition shown in Table 7 below, a powder of a solid electrolyte was
`obtained,
`
`feeample 14}
`
`fOOG7]. Yrium-stabilized zircorda with amolarratio of 2p -Y = 1.02 0.38 was synthesized using zirconium oxide (21O.}
`and yttrium oxide (¥,.O,) es rew materiats. In the same way as in Comparative Example 1 except that raw materials
`including fhe yitjum stabilized zirconia and Whium carbonate (Li,0O,), and armmonium dihydrogen phosphate
`INKZH.PO,) were weighed so as to have the compasiion shown in Table 1 below, a powtler of a soli electrolyte was
`obtained.
`
`(Example 15}
`
`fo062] Ytiriurn-stabilized zirconia with a molarratio of Zr: Y= 1.60. -.0.40 was synthesized using sircenkum oxide (2°0.)
`
`

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`and yithum oxide (y¥,O3) a6 raw mieteriais. In ine same way as in Comparalive Example 1 except that raw materials
`including fhe yttdum stabilized zirconia and Whium carbonate (LiglOs), and ammonium dihydrogen phosphate
`iNH,HPO,) were weighed 50 as to have ine compasition shown in Table 1 below, a powdeler of a sold afectrolyte was
`obtained.
`
`(Example 16}
`
`[8063] Ytiriurm-stabilized zirconia with a moterratio of Zr Y= 1.93 / 0.08 was synthesized using zirconium oxide(2rQ2}
`and yttrium oxide (¥,O.) as raw materials. in the same way as in Comparative Example 1 except that raw materials
`including the yttrium stabilized zirconia and alurninum oxide (ALO), lithium carbonate (LinCO,), and aramonium dihy-
`drogen phosphate (NH,HPO.) were weighed so as ta have the composition shown in Table 1 below, a powder of a
`solid electrolyte was obtained.
`
`(Example 17}
`
`fo064] Yttriurn-shabilized zirconia with a molarratio of fr oY = 1.64 : G06 was synthesized using zirconium oxide(2rO.)}
`and yithumt oxide (¥5O.) as raw matenais. In the same way as in Cornpearative Example 1 axcepf thal raw materiais
`including the yttrium stabilized zirconia and aluminum axide (ALO), lithium carbonate (Li,CO,), and ammonium dihy
`drogen phosphate (NH, HoPO,) were weighed so as to have ihe composition shownin Table 1 below, a powder of a
`solid electrohvte was obtained.
`
`{Example 13}
`
`foees] Ytirurn-shabilized zirconia with a molarratio of re: Y = 1.44 : 0.05 was synthesized using zirconium oxide(2rO4}
`and yitnum oxide 4,0.) as raw materials. In the same way as in Comparative Example 1 except that raw materials
`including the ytirium stabilized zirconia and germanium oxide (GeO,}, lithium carbonate(Li,CO.), and aramonium di-
`hydrogen phosphate (NH,HsPO,.} were weighed so as fo have the compasition shownin Teble 1 below, a powderof a
`salid electrolyte was abteined.
`
`ts&
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`fExampie 19}
`
`fOOGE] Yitriunn~stabilized zirconia with a molarratio of Zr: Y= 1.97 : 0.05 was synthesized using zirconiumoxide (ZrOo)}
`and yitrlum oxide 6',O.) as raw materiais. In the same way as in Comparative Example 1 except that raw materials
`inchiding the yttrhumstabilized zirconia and Gbanium oxide (TiO.)}, thiumcarbonate (Li,CO,), and ammoniumdihydragen
`phasphaie (NH, HoPO,) were weighed so as to have the composition shown in Table 1 belaw, a powder of a solid
`electrolyte was obtained.
`
`tExaniple 20)
`
`‘YHrium-stehilized zirconia with a molar ratio of Zr Y= 1.99 | 0.06 was synthesized using zirconiumoxide (76rO>}
`fO067]
`and yilrium oxide (Y5O.) as ru materiats. in the same way as in Comparitive Example 1 except ihal raw materials
`including the yttrhum stabiized zirconia and vanadium oxide (/5;O.)