B Ovfide sieopean § HABE
`
`B farupatechex
`atari
`g Etrromeats
`B Potant Offies
`
`$
`i
`ERE
`t
`PETE
`
`(11)
`
`EE UES BEE:
`t
`SEE
`SR SSR
`y
`rt
`q
`8
`Pu
`Ry
`SPREE
`SEN
`EEE
`‘
`A
`i
`SEE
`SR
`Saree
`Sm
`¥
`+
`q
`SRC SUES SE BS
`
`
`
`EP 3 496 202 Al
`
`(42)
`
`EUROPEAN PATENT APPLICATION
`published inaccordance with An. 1834) EPC
`
`(43) Date of publication:
`42.06.2879 Bulletin. 2679724
`
`{21} Application number. 17836688.4
`
`{22} Date of filling: 67.07.2017
`
`(84) Designated Contracting States:
`AL AT BE BG CH CY CZ DE DK EE ES FIFR GB
`GRHR HUE IS IT LILT LU LV Mi ME MT NL NO
`PLPFRO RS SE SISK SMTR
`
`Designated Extensian States:
`BA ME
`Dasignated Validation States:
`MA MD
`
`(30) Priority: 04.08.2016 JF 2076183736
`GBH6.20T7 JP POAT 113102
`
`(74) Applicant: Panasonis Intellectual Property
`Management Co. Lid.
`Osaka-shi, Osaka $40-6207 LIP}
`
`{723 Inventors:
`* ASANDS Tetsuya
`Osaka 540-8207 {JP}
`
`
`
`.
`{67} Intch
`HOM TOH0S62 2M BoE ppg nen
`HOIM 4173 21000)
`HOIM fojos2 Geen
`HOM 10/0585 C0062
`
`(85)
`
`international apoticatian qurnber:
`PCTLIP20 7/0249 34
`
`(87)
`
`intematonal publination number:
`WO BM 8025582 (00:022076 Gazette 2075/06}
`
`SAKAI Akihira
`
`Osaka 540-6207 {JP}
`OMUCHI Satoru
`
`Osaka 540-6207 (IP)
`SAKAIDA Masashi
`
`Osaka $40-6207 (UP)
`MIYAZARI Akinobu
`
`Osaka 540-6207 (IP)
`HASEGAWAShinya
`Osaka 540-6207 (IP}
`
`Representative: Elsenfahr Speiser
`Patentanwalte Rechtsanwalte PartGmbB
`Postfach 1060 78
`
`28060 Bremen (DE}
`
`(64)
`
`SOLID ELECTROLYTE. MATERIAL, AND CELL
`
`{57}
`
`in known technologies, itis desired fo realize a solid electrolyte meierial having a high lithun: ion conductivity,
`A solid electrolyte material according fo an aspect of the present disclosure is represented by the following Cor
`positional Formula (1k
`
`LigY%e
`
`Formula (1)
`
`where, 0 « 2 < 2 is satisfied: and X represents C} or Br.
`
`EP3496202Al
`
`Fred bydouve, 75004 PARIS (FR?
`
`(Cont. next page}
`
`

`

`EP 3496 202 At
`
`FIG. 1
`
`

`

`w
`
`t5
`
`20
`
`25
`
`andva
`
`HadmH
`
`43
`
`ote.at
`
`EP 3.496 262 At
`
`Description
`
`Techsingt Field
`
`{8007} The present disctosure relates io a solid slectrobfe material and a battery.
`
`Background Act
`
`{8002}
`{8003}
`
`PYL } discloses an all-salid battery using a sulide sohd electralyte.
`PTL 2 discloses an all-solid battery using @ halide containing indiutn as-a-solid electralyte.
`
`Citation List
`
`Patent Literature
`
`fOO4]
`
`PTL 1: Japanese Unexamined Patent Apsligation Publication No. 2074-129312
`PTL.2: Japanese Unexamined Patent Application Publication No. 2008-244734
`
`Summary of Invention
`
`Fachnical Problen
`
`fOG0S]
`
`in known fechaplogies, 1 is: desiread-te realize a sold sleciraiyte material having a high Hhium fon conducihaty.
`
`Salation te Problern
`
`{8606] A solid electrolyte matetial according to an aspect of the present disclosure is represented by the following
`Compositional Formiuda<T:
`
`Ling.Vets
`
`Formula (7)
`
`where, 0 <2 < 2 is salished:; and X represents Ci or Br,
`
`Advantageaus Effects af lnventian
`
`{8607] According to the present disclosure, a solid eisctrolyte material having-a high ithium ion conduntivity can be
`achieved.
`
`Brief Description of Drawings
`
`{0008}
`
`Fig. t is a cross-sectional view Hlusivating & scheriatic structure of a battery 1000 in Embodimerd 4.
`Fig. 2. is a perspactive view iustrating the crystal structure af a LisErBrs struchirp.
`Fig. 3 is @ perspective view ilhustrating the crystal structure of a LLErCl, structure.
`Fig. 4 is.@ schematic view dlustrating a niethod for evaluating. ionic canductivey.
`Fig. Bis a.graph showing temperature dependence af the jonic conductivity of solid electralvies.
`Fig. 6 is a graph showing XRO patterns of solid elacitralyle materials.
`Fig. 7 is a-graph showing inital discharge characteristics.
`Fig. & js 2 perspective view Hustrating the crystal structure of a LigYbCly structure.
`Fig. 8 isca graph showing temperature dependance of the ionic conductivily of salid elactraivies.
`Fig. 10 js.4 graph showing an XRD patiern of a solid electrolyte material.
`Fig. }1 is a graph showing initial discharge charactenstics.
`Fig: 12 ts a graph showing ah XRD pattern of a solid electrolyte material,
`
`

`

`Description of Embodiments
`
`EP 3.496 262 At
`
`iO009}
`
`Ermbodimnancis of the present disclosure will nowbedesenbed with reference to the drawings.
`
`{Embodiment 1}
`
`[8040]. The solid clectrofyie materialin Embodiment 1
`Formula (2):
`
`is a compound represented by the fallowing Campositional
`
`w
`
`Lis¥Xg
`
`Formula (2)
`
`t5
`
`where X represents CH ichborine} or Br (bromine}.
`014] According te the siruchure menbaned above, a solid electrolyte material (halide satid alecbolytic material} having
`a high Ithium.ion conductivity can. be achieved, [n addition, a solid elactrotyie matenal having a. structure stable in.an
`assumed operation lenyerature range {6.g., a range of -30°C fo 80°C) of a battery can be achieved. Thatis, the satid
`aiecirolyte maternal of Embodiment t does mot have a structure (e.g: the-stnuchine in PTL 2} in which the phase iransifion
`jemperature is.-present within the operation lemperature range of the battery. Consequently, even in an environment
`with temperature change, phase fansition does not occur in the operation tamperaturerange of ihe battery, and a-high
`ionic conductivity can be stably maintained.
`{8672] According to the structure described above, an all-solid-state secondary battery having-excellent charge and
`discharge characteristics can be achieved by using the spl efectroiie material of Embodiment 1. In-addition, an alt
`sulk-state secondary battery nat containing sulfurcan be achieved by using the solid electrolyte material af Embodiment
`1. Thatis, the solid electrolyte material af Embodiment] does nat have a siniohire (e.g. ihe structure in. PLT 7) generating
`hydrogen sulfide when exposed ts the atmosphere, Accordingly, an albsalid-siaie secondary battery not generating
`hydrogen sulfide and having excellent safely can be achieved.
`{6042] The solid electrolyte material in Embodiment 1 may include « orystal phase. Examoles of the orystad phase
`include a first crystal chase and. a sacend crystal phase described below.
`{O0%4] Thatis; the solid siectrotyie material in Embodiment 1 may include a first crystal phase.
`{8015]
`in the first crystal phases, the arrangernent of halogen X is the same as that of Brin Li,Eriir, (hereinafier, also
`expressed ac LEB) having. a crystal stricture belonging fo space group G2im.
`fO018] According to the structure described above, a solid clectrolyie maternal having a higher ithiurnjon conductivity
`can bs achieved..Sgeciically, a crystal structure ike the firstcrystal phase allows X to be more siranglyatirected to ths
`periphery of Y. Consequently, a path through which lithium ions diffuse is formed. Accordingly, the ithium ion conductivity
`is further improved.
`[6017]
`Fig. 2 is a perspective view Nustating the crystal structure of a LisErBre stricture.
`f018] As shown in Fig. 2, the LijErBr, stricture (LEB structure) has monoctinic symmetry and js a crystal structure
`belonging io space: group O2/m. The details of the atomic arrangement are available inthe Inorgario Grystal stricture
`databases CSD}.
`fe0439] The first crystal phase having the same Naingen arangertent.as thal of the LEB stricture inchides, ina uni
`cell, lwo of ihe same compositions represented by Compositional Formula (2).
`[8020]. The fettice constants of the uni call defined by the LEB siructure an a= 8.9 ta 7G angstrom, b= 34.9 fo 13.4
`angstrom, c = 6.840 7.6 angstrom, a = 90°, 8 = 109°, and y= 80°.
`{8024].The LEB structure can be identified by structural analysis using X-ray diffractametry. When the measurement
`is performed by a 4-26 method using Guckerays Ovavalengthy 1.5405 angstram and 1.5444 angsirem} as the X-ray,
`strong peaks are observed within the ranges of diffraction angle 28 values of 25° is 28°, 297 to 327, AY* to 467, 49° to
`55°and 51° to 58°,
`{0022] The solid electrolyte materialin Embodiment 1 may satisly |)eecysoy/lugagzon) < 0-01.
`{6023} Herein, heoong tepresents the A-ray diffraction intensity of @ first crystal phase plane comesponding to the
`(205) plane in the crystal structure of LigErBr,:
`fhez4] Renesas represents the X-ray dNfracton intensily of a first crystal. phase plane corresponding tothe (170) olane
`inthe crystal structure of LigErBr,.
`[0025] According io the structure described above, a aolid electrolyte material having a higher dthiumjon. conduativity
`canbe achieved. Specifically, imeguhar arrangement of Y can be achieved: Consequenily, the conduction path of hitium
`ions is three-dimensionally connected. Accordingly, the jithium jon conductivity is further improved.
`{8026} As described abova, the arrangement of cations of the salid electroiyie material in Emoodiment t-need not be
`the same as ihe arrangement of cations in the LEB structure. That js, at least part of ¥ (yttrium) and atleast part of Li
`maybe imegidarly arranged.
`[6027] The rregulanty of the arrangernent of cations can be evaluated by the above-mentioned: intensity ratio
`
`20
`
`25
`
`andva
`
`HadmH
`
`43
`
`ote.at
`
`

`

`w
`
`t5
`
`20
`
`25
`
`andva
`
`HadmH
`
`43
`
`ote.at
`
`EP 3496 202 At
`
`“emiahepeodyif the XRD pattern.
`[e028] Wher the arrangement of¥ is reaquiar, Lear nyenonm = about O.0d(about 2%). The value of |cer toyleso
`decreases with an increase in ireguladty. As desorbed above; Feacig/lesaco; « G01 (9%), sufficiently kregular
`arrahngenand of Y can be achieved.
`{8029} The solidelectroiyie material in.Embodiment 1 may satisly FWHM,/23e, > 6.015:
`{00230] Herein, FWHM, represeris the full width at half maximurn of an X-ray diffraction peak of a first crystal phase
`plane oorespanding to the (200) plane in the orystal structure pf L.ErBr.
`f6031]
`In the expression, 260, denotes the diffraction angle af the centerof the X-ray diffraction peak (peak central
`yahie}.
`[8022] According fo the structure described above, 2 solid electralyte material having a higher lithium ion canductivity
`oan be achieved. Specifically, a nanunifonn iatice constant can. be pravided. Consequently. a regan having @ spread
`in the fatiice is formed. Accordingly, the lithium ian condustivity is further improved.
`{8033} As described above, the laiice consiantofthe sald electrolyte materialin Embodiment | need nal be canipletely
`uniform. That is, the tatice constant may have seme nomunvorniy. Speciinally, the laine constant disinibiudion may
`have a hal width at half maximuny of about 1% of more.
`fOG34]
`in the solid electrolyte maternal of Embodiment 1, the structure of the first crystal ghase may he distorted, and
`the atoms may be arranged at slightly different atomic positions.
`{8035} The solid clactralyte maternal in Embodiment 1 may inchide.ahelerogensaus orystal phase having a-crystal
`structure diferent fram that of the first crystal phase.
`{0026]
`in such a case, the heterogeneous crystal phase may lie belween the first orysial phases.
`[8037] According tc the structure described above, a solid electrolyte material having a higher ithiurn ion conductivity
`can be achieved. Specifically, the conduction of fithium ions between the first crystal phases is enhanced by the heter-
`agensocus orysial phase. Accardingly, the lithium ion conductivity is further improved.
`{8038} The solid electrolyte raterial in Emvbodiment 1 may include an amorphous phase.
`{8039]
`in such a case, the amorphous phase may le between the first orysial phases.
`{6040] According to the structure described above, a solid alectralyle material having a higher Hthiura hn conductivity
`can be arhieved. Speoiically, the conduction ofiithium ions betweenthe frstcrystal phases is enhanced by the amerphous
`phase. Accordingly, the ithhum jon conductivity is hucther imeroved.
`{0044] The solid siectrolyte material in Envbodiment 1 may include a’secand crystal phase:
`{0042]
`in the second crystal phase, ihe arrangement of halogen X is the same as that of Glin Li,Esl, (hereinatter,
`also expressed as LEC) having # crystal structure belonging to space.group F-3mi4,
`{0043}. Arcording to the structure described above, asnlid electrolyte maternal having a-higher lithiumion conductivity
`can be achiaved. Specifically, a crystal struchuire like the second erysial phase allows X to be more strongly altracted to
`ihe penphary of Y. Consequanily, a path through which iithium jons: diffuse is foamed, Accordingly, the ithhim jon
`conductivity is further improved.
`(8044)
`Fig. 3s a perspective view Hustrating the crystal structure of a LIZErCl, structure.
`fG045] As shown dn Fig... the LigerCh, structure {LEC striclura} fas trigonal symmetry and is a crystal structure
`belonging fo space group P-3ort. The details of the alornic arrangement are available in the inorganic crystal structure
`daiabase GOS0).
`[6046] The second orystal chase having the same halogen arrangement as that ofihe LEC structure includes, in a
`unit calls, three of he same compasilions represented by Gompasitional Formula (2).
`{8047] The lattice constants of the unit cell defined by the LEC struchwe-are a = 10:97 fo 11) angstrom, b= aq o=
`6.9 to £2 angstrom, a = 90°, f = 90", and y = 120°.
`e043] The LEC structure can be idantfied by structural analysis using M-ray diffractometry. When the measurement!
`is performed by a 5-26 method using Cu-Ka rays (wavelength: 1.5405 angsironvand 1.5444 angsirord) asthe X-ray,
`strong paa@ks are observed within the ranges of diffraction angle 26 values of 28.8" to 32°, S8.S° to 41 7°, 46.5" ta 50.4")
`and 50:8" to G5.4",
`[0049] The solid electrolyte material in Ermibodinient 1 maysatisfy kcopoyliecmog «9-4.
`[6050] Herein, iieoisns; 8 the Xray diffraction intensity ofa second crystal phase plane correaponding te the (303)
`plane in the crystal structure of LisErCly.
`[0054]
`lec qig) is the X-ray diffraction intensity af a second crystal phase plane corresponding to the (110) plane of
`the crystal structure of LigkrCl,.
`i8052] According te the structure described above, a sclid-clectroiyie material having a higher Hhivm jon conductyily
`oan be achieved. Specifically, irraguiar amangernent of ¥ oan be. achieved. Cansequently, the conduation path of ithium
`1ons ig Three-cimensionally candacted, Accordingly, the idhium- ion. conducivly is funther improved,
`[0053] As deveribed above, ihe arrangement of oaliona of the solid electroiyie material in Embodiment 1 need not be
`the same as the arrangement of cations af the LEC siructure. That is, at least part of Y and at least nart of Li rniay be
`irreguiaiy arranged.
`
`

`

`w
`
`t5
`
`20
`
`25
`
`andva
`
`HadmH
`
`43
`
`ote.at
`
`EP 3496 202 At
`
`{8054] The regularity of the esrrangement of cations can be. evaluated by the above-mentioned. intensity ratio
`“cescrtoylesigog; fr the XRD pattern.
`{OSS} Whanthe afrangeamentory is reguiar, Leeroyieeross 2 about h.45 fabautds%} . The vahie of heon 1OFRECON
`decreases with an increase in irreguianty. As described above, # lleemrovhecisog < 0.50 (80%), sufficiently ireguiar
`arrangement of Y canbe achieved.
`{8656] The solid slectrolyte material in Envbodiment 1 may safisfy FWHM)/2ec, 2 0.015.
`{OG57] Herein, FWHM, represents the fil width at half maximum .of an x-ray diffractionpeak ofa second crystal phase
`plane corresponding to the (203) plane in the crystal structure of LIsErOl,.
`(8058)
`in ihe expression, Zc, denotes the diffraction angle at the center of fhe K-ray diffraction peak (peak central
`value}.
`{OUSS} According ta the structure descobed above,a salid slectraiyie material having a higher Hhium jon canductivigy
`oan be achieved. Specifically, a nonuniformlattios constant can be provided. Consequendly, a region having a-lattice
`spread is formed. Accordingly, the Nhtern jon conductivity is further improved.
`{0060} As described above, the laltice constant ofthe solid electrolyte matenialin Embodiment } need nal be canipletely
`uniform. That js, the lattice constant may have same nonuniformily. Specifically, the iniice constant distribution may
`have a fall width at half maximo of about 1% or more.
`[6061]
`in the solid electralyte material of Ernbadirnent 1, the structure of the second crystal phase raay be distorted,
`and the ators may be arranged at slighily diferent atomic pasifions,
`{0682} The solid electrolyte material in Embodiment 1 aay include a heterogeneous crystal phase having.a crystal
`structure differant fram that of the secand crystal phase.
`f@063]
`in-such'a case, the heterogeneous crystal phase may lie Setween the second crystal phases.
`fO064] According to the structure described above, a solid clectrolyte maternal having a higher ithiurnjon conductivity
`can be achieved. Spacifinally, the conduction of Mhiuri ions. behveen te second crystal phases is .eshanced by the
`heterogeneous cryatal phase. Accordingly, the Wihium ion conductivity is further improved.
`jG06S] The salid eleciratyie maiedalin Erabedirment 7 may inchide an. armiorphaus phase.
`{6068]
`in such a case, the second crystal phase ray fie between the second crystal phases.
`{8067} According to the structure desorbed above, a solid sleciralyte matenal having a higher thiumion conductivity
`can be achieved. Specifically, the conduction of Bthiurn tars behveen. tre-second crystal phases is enhanced by the
`amorphous phase. Accordingly, te lithium ton conductivity is further improved.
`[8068] The solid slectrohte material in Ercboadimenit I may Have any shape, such as an acicudar, soherical, ‘or oval
`spherical shape. For example, the solid electrolyte maternal in Enthodiment 1 may be in‘a particle form. A plurallly of the
`particles may be laminated and then formadinio a pellet or plate by pressurzaian,
`{0069]
`For exarnpie, when the solid electrolyte material in Embodiment 1 is in a particle (e.g., spherical) form, the
`median dlameter may be 0.7 p.m or more and 100 pum or less.
`[6070]
`in Embodiment t, the median diameter may be 0.5 im or more and 10 pm or jess.
`{8071} According to the siruchire described above, the ionic canductivily can. be further Increased. in.addition, a more
`sabsfactary dispersion state of the. solid elactratyie maternal of Embodiment 1 and an active matenafor ihe tike can be
`farmed:
`[8072]
`material,
`[8073]. According te the structure described above, a more satisiactory dispersion siate of the solic electrolyte material
`of Embodiment 1 and an active material or the like can be formed.
`
`in Embodiment 1, the sold clectolyte material may have a median clameter smatier than thai of ihe active
`
`<Mathod for producing solid electrolyte material
`
`{8074} The solid elecirohite material in Embodiment t can be produced by, for example, ihe following methad.
`{2075} Raw nraterial powders of binary halides are prepared af a blending ratio giving = target commusition. For
`example, in the case.of producing LIsYCi, LiCl and YCare pregared at a molar ratho of 3: 1.
`[6G76]
`in such a case, X in Compositional Formula (2) can be determined by selecting the tyges of the raw material
`powders. The rawmaterial powders are sufficiently mined and are then mixed, pulvedzed, and reacted with each other
`using a rmechanoachemical milling process..Atematively, ihe raw material powders are sufficiently mixed and may be
`thensinfered in. vacuurn.
`
`S077] Consequently, a sold electrolyte matenal having a orysial phase described above is given.
`{6078] The structure of the crystal phase (crystal structure) of the solid electrolyie material can.be defermined by
`adjusting the macton methad and reaction conditians for the raw maternal powders.
`
`

`

`{Embodiment 2}
`
`EP 3.496.262 At
`
`w
`
`t5
`
`20
`
`25
`
`tayva
`
`HadmH
`
`43
`
`ote.at
`
`iO07S} Ermboadinaci 2 wil now be described. The dascrigtion overlapping with Embodiment 1 described above is
`omitted as appropriate.
`{8080} The solid alectrohte material in Embodiment 2 is a compound represented by Compositional Ferma (1):
`
`higas¥Xe
`
`Formnuta (1)
`
`where, 0 < 2 < 2 js satisfied: and:X represents Cl or Br.
`{8084} Accordingte the structiire mentioned above.a solid electralyie maternal (halide solid electrolytic material} having
`&high Mhigm.jon conductivily can be achieved. In addition. a Solid electrolyte material having a structure being stable
`in the assumed operation temperature range (e.g, a range of -30°C to 80°C} of the batiery can be achieved. That is,
`the said Glectralyie material af Embodiment 2 does nat have a structure {¢.g.. the structure in PTL 3} in which the shase
`transition iemperature is present within the aperalion lamperature range of the battery. Gansequenily, even in an aavi-
`ronment with temperature change, phase transitien does not occur. in the aperation teraperature rangeuf the battery,
`anda high-ientc conductivity can be stably maintained:
`{6082] According tothe structure described above, an al-salid-siaie secondary battery having excellent charge and
`discharge characteristics can. be achhaved by using the salid elactralyte material of Embodiment 2. tq-add#ion, an all-
`solid-state secondary battery nol containing sulfur can be achieved by using the salid-electrolte materia! Embodiment
`2. Thatis, the solid electrolyte material of Embodiment 2 does not have a structure (e.g. te struchure in PLT 1h generating
`hydrogen suffide when exposed to the atmosphere. Accordingly, an al-sold-state secandary battery not generating
`hydrogen sulfide and having excellent safety can be achieved.
`[8083]. The solid slectrolyte material in-Embodiment 2 satisfies 0.75 < z= 1.5.
`{8084] According te the struchure described above, asalid electrolyte material thalicle solid electralytic material) having
`a higher thaiion conductivily can Ge achieved. in addition, an all-solid-stale secondary ballery having more excellent
`charge.and discharge characteristics can be achieved.
`{8085] The solid electrolyte material in Embodiment 2 satisfies 1 <2 < 1.25.
`{8086} Accorcdingte the structure described above, a solid electrolyte material (halide solid electrolyte material) having
`@ higher lithium jon conductivity can be achieved. In addition, an all-sulid-state secondary batiery having more excellent
`charge. and discharge characteristics can be achieved.
`{O08T] The solid electrolyte material in Embodiment 2 may include & crystal chase. Examples of the orystal phase
`include a first crystal phase anda thind crystal phase described below.
`{G8028] That is, the solid electrolyte material in Embodiment 2 mayinclude a first-crystal phase.
`[0009]
`in the first crystal phase, the arrangement of hatagen.X is the same as that of Brin LijErir, (hereinafier, alsa
`expressed as LEB) having.a orystal structure belonging fo space group CZfim.
`{8090] According to the structure desorbed above, a solid sleciralyte matenal having a higher thiumion conductivity
`can be achieved. Specifically, a crystal structure like the first crystal phase allows X fo Be mare sirangly attracted to the
`periphery af ¥. Consequently, agath through which ithigm ions diffuse is formed. Accordingly, the lithium jon conductivily
`is further iniproved.
`[6097] As shown in Fig. 2, the Li,Er@r, structure (LER siructure} has monoolinic syrameiry and is a Srystal structure
`belonging io spare group Clim. The details of the atomic arrangement are avaiable in the inorganic crystal sirichire
`database (}CSD}.
`[8692] The first crystal phase having the same halogen arrangement as that of the LEB alructure includes, in 3. unit
`call, lwo of the same composition represented by Compositional Formula (1).
`{6093] The latlice constants of the unit cell defined by the LEB structure are 4 = 6.9 fo 7.6 angstrom, b= 11.940 134
`angsirom, ¢ = 6.8 to 7.5 angstrom, o = 90°, B= 109°, and y=.B8".
`{0694] The LEB structure can be identified by structural analysis using X-ray difiractametry. When the measurement
`is performed by a 6-26 method using Girko rays dvavalength: 1.9405 arestrom and 1.5444 angstrom} as the x-ray,
`strong peaks are observed within the ranges of diffraction anule 29 values of 25” to 38°, 22° to 3B, 41° to 477, 49% to
`§5°, and 51° to 58°.
`[0095] The solid electrolyte material in Embodiment 2 may sutisly kcecsyoy/lesyanny * 8.07.
`f0086] Herein, legiogg; Pepresents the X-ray diffraction intensity of a first crystal phase plane corresponding tothe
`(200) plane in the crysial structure of CisErBr,.
`P8297]
`tLepesem Pepresents the Cray diffraction intensity of a firstcrystal phase plane corresponding to the (110) plane
`ni fhe ceystal structure of LizErBr,.
`[0098] According fo the slructure described above, a solid electrolyte matenal having a higher Hthiumion conductivily
`oanbe achieved. Specifically, irregular arrangement of Y can be achieved. Conssquanily, the conduction path of ithium
`ions js three-dimensionally connected. Accordingly, the lithium jon canductivily is. further improved.
`
`

`

`w
`
`t5
`
`20
`
`25
`
`andva
`
`HadmH
`
`43
`
`ote.at
`
`EP 3496 202 At
`
`{0099) As described above, the arrangernent of cations of the solid electrolyte material in Embodiment 2 need not be
`the same as the arfangement of cations of the LEB stracture. That is, atleast part of ¥ and at isast pact of Li may be
`irregulady arranged.
`6700] The irregularity of the arrangernent of cations can be evaluated by the above-mentioned intensity ratio
`“igaprioylenaoayin the ARD pattern.
`i0101] When the arrangementot ¥ is regular, hea rioego = ADOuLO.02 (about 2%). The value ofcary wy'lemcandy
`decreases with an increasein imegulariy. As despribed above. HJyese; syhesiics © G01 (1%), sufficiently irregular
`arrangement of ¥ can be achieved.
`a Oo
`fOi2] The solid electrolyte material in Embodiment 2 may satisly FWHM,/20c, = 0.015.
`f0103] Herein, FWHM, represents the full width at half maximumof an X-ray diffraction peak of a firal crystal phase
`plane corresponding to the (200) plane in the crystal structure of LijErBr,.
`$0704]
`in the expression, 200, denotes the diffraction angle al the center of the X-ray diffraction peak (peak central
`wale).
`{O25}. According to the structure described above, asnlid electrolyte maternal having a-higher lithiumion conductivity
`can be achieved. Specifically, a nonuniforn lattice constant'can be provided. Consequently, a region having a jatiice
`spread is farmed. Accordingly, the idhhemnion conducliviy is further improved.
`{6108] As described above, the latlice Canstantof the auiid electrolyte material in Embodimernd2 need. not be completely
`untorm. That is, the fatice consiant may have seme nonuniformily: Specifically, the latiice cansiant disinbution may
`have a full width af half meximuny of about 1% ar more.
`{Q407]
`in the solid electrolyte material of Ersbodiment 2, the structure of the first crystal phase may be distoried, and
`the atonis may be arranged at slightly different atomic pasilions.
`[6708] The solid electrolyte material in Embodiment 2 may include.a heterageneous crystal phase having a crystal
`structure diferent fram that aftha first orystal phase.
`{0109]
`in such a case, ihe heterogensous crystal phase may lie between the first crystal phases.
`jO170] According to fhe structure described above, a said electrolyte. material having a higherhiloton conduchyily
`oan be achieved. Specifically, the conduction of lithium jonsbetween thé first crystal phases is anhanced by the heater
`ogensous crystal phase. Accordingly, the Hihtum jon conducobuly is further improved.
`8143] The solid electrohte material in Embodiment 2 may Include.an amorphous phase.
`{Qtt2]
`in-such a case, the amorphous phase may lie between the first crystal phases.
`{8443] According to the structure described above, a sald electrolyte material having a higher Hthiurn jon conductivity
`oan be achieved, Specifically, the conductionof lithiurn ians between the first crystal phases is enhanced by the amorphous
`phase. Accoringly, the Ithhuerian conductivity is hucther imgroved.
`{Gt74] The. solid electrolyte material in Embodiment 2 may include a third orystal phase.
`[0415]
`in the third crystal phase, the arrangement of halogen % is the same as that of Clin Li,YbGI, (Hereinafter, alsa
`expressed as LY} having a.crystal structure belonging to space group Prima,
`{8446] According to the structure desorbed above, a solid sleninalyte matenal having a higher iithiumion conductivity
`can be achieved. Specifically, a crystal structure {ike the third orystal phase allows % to be more strongly attractedto
`the perishery of Y. Consequently, &@ path through which jithhim ions diffuse is farmed. Accordingly, the Hittiam ian
`conductivity is furtherimproved.
`[6117]
`Fig. Sis a perspective view Nustrating the crystal structure of a LigybCl, structure.
`{O98}. As shown ie Fig..8, the Lu,YOU,siructure (LYsiracture} has orthorhombic syrnmebry andis a crystal struciiee
`belonging fo space graup Pama. The details of ihe gliomic- arrangement are available in the inarganic'‘crystal strusiure
`database CSD}.
`[O14S] The thid crystal phase having the same halogen arrangement as that af the LYC siruchire includes, in a unil
`eell, ihree of the same canposilions represented by Compasitional Formula (1}-
`{0120} The lettice constants. of the unit cell defined by the LYstricture are a = 12.8-to TSS angsiram, b = 11.1 to
`12.6 angstrom, and c= 5.90to 6. 10 angstrom.
`i8t27] The LYC structure canbe identified by sinuctural analysis using X-ray diffractometry. When the measurement
`is performed by a 4-29 method using Cu-Ka rays (wavelength: 14405 angstrom and 1.5444 angsiram} as the X-ray,
`strong peaks are observed within the ranges of difraction angle 26 vahies of 29.8 ta 32", 38.5° to 417°, 46.5° i 504°,
`and B08" te §5.4°,
`{O122] The solid slectralyte material in Eovbodiment 2 may salisly FWHMs/(28ec5 2 G.015.
`[0123] Herein, FWHM, represents thefull width al half maximum of an X-ray diffraction peak of a third crystal phase
`plane corresponding to the (231) plane in the crystal structure of LIAYbOl,,
`fii24]
`In the expression, 20, denptes the diffraction angle at the center of the Kray diffraction peak (peak central
`value}.
`[8425] According te the structure described above, a adiid elactrofyte material Having a higherIhium ion conductivity
`oan be achieved. Specifically, a nonuniformlatioe constant can be pravided. Consequently, a region having a lattice
`
`

`

`EP 3496 202 At
`
`t5
`
`spread is formed. Accordingly, the lithiumjon.conductivily is further imoroved.
`{O426} As described above, ine lattice canstant of ihe salid electralyie material in Embodiment 2neednothe sompletely
`uniform. That is, the lattice constant may hawe same nonundormity. Specifically, the lattice constant distibuban may
`have afull width at-half maximum of about 1% or mare.
`HE] i ihe solid elestrohte material of Embodiment 2, the structure of the thirc crystal phase may be distorted, and
`the alome may be arranged ai-slightly diferent atomic pasitions.
`{0t28]. The solid siecirolyte material in Embodimant-2 mayinclude a heterogeneous crystal phase having a crystal
`structure different fromthat of the third crystal phase.
`{8129}-In-such a case, the -heterogansaus crystal phase may fe between the third crystal phases.
`w
`(8420) According fo the structure described above, 2 solid electralyte material having a higher lithium ion canductivity
`can be achieved, Spectically, the conduction of lithium ions belween the thicd crystal phases is enhanced by the hater
`ogenecus crystal chase. Accordingly, the thium ton conductivity is further improved.
`f0434] The solid alectrolyie material in Embodiment 2 may include an amorphous shase.
`[8332].
`In sucha case, the amamphous phase may He bebwaen the thie orystal phases.
`{0433] According fo the structure described above, a solid electrolyte matenal having:a higher thin ion canductivity
`oan. be achieved. Specifically, the conduction of ithium jens between the third crysial phases is eanhanced by the amer-
`phous phase. Accordingly, the ithiim jon conductivity is further improved.
`{8134} The sold electrolyte matenal in Embodiment 2 may have any shane, such as. an acicular, spherical, or aval
`spherical shape. For example, the solid electrolyte material in Embodiment 2 may be ine particie form. A plurality of the
`oarlicles may be laminated and then formed info a pelletor plate by pressurization.
`[835]
`For example, when the solid electrolyte material of Embadiniant.2 is In a particle {e.9.. spherical) form, the
`median diameter may be 0.1 pm or more and 100 gra or less,
`{O336}].
`in Embodiment 2, the mediandiameter may be 0.5 pm or more-and 10 p.m orless.
`{8427] According to the structure described above, the ionic canductivity can be further inoreaved. In addifion, a more
`satisfactory dispersion siate of the solid electrolyte material of Ernbadiment 2 and an active material ar the like. can be
`formed.
`
`20
`
`25
`
`{8738]
`rnaterial,
`
`In Embadimerit 2, the solid electrolyte material may havea median diameter smaller than that of the active
`
`andva
`
`{0439] According to the structure described above, a mare satisiactory dispersion state of the solid electrolyte material
`of Embodiment 2 and an active materialar the he oan be formed,
`
`«Method for pracducing solki electrolyte material>
`
`HadmH
`
`43
`
`ote.at
`
`fet40] The sald electralyie material in Ernbodimant 2 can be