`
`B kasupatsches
`motatot
`B
`Eurouecti
`B Potant Offies
`B Ofiey soraeden §
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`a
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`(1%)
`
`EP 3 745 422 A‘
`
`EUROPEAN PATENT APPLICATION
`published in accordance with Art. 15344) EPC
`
`(433
`
`Date of publication:
`$2:492.2020 Bulletin 2020/49
`
`atm hh woe Ae
`
`Agpicdtiod number 82802720.4
`
`Date. of Ming: P4.44.2048
`
`io net
`
`ECL:
`HOTB 1/06 2ORON
`COIG 25pg Boe
`HOM 16,059 (208007)
`
`COIF 17/09 AND
`HOIM 4.63 2006-01)
`HOIM 16/0562)201)
`
`international application number:
`PCTIJP203 BIA2062
`
`}
`
`infemational publication numbec
`WO 2019446219 (01.98.2019 Gazette 2079/34}
`
`Designated Contracting States:
`AL AT BE BG CH CY C2 DE OR EE-ES FIFR GB
`GRHR HUTIEISITLILT LU LV MC MK MYT NLNG
`PLPT RO RS SE SISK SM TR
`
`Designated Extension States:
`SA ME
`
`Resignatad Vatdation States:
`KH MA MO TN
`
`Priory: 26.04.2012 JP 2078641536
`
`Apticant Panasonic Intellectual Property
`Management Ca., Lid.
`Osaka-shi, Osaka $40-6207 {JP}
`
`inventors:
`SAKAIDA Masashi
`Osaka-shi
`
`Osaka 540-8207 (JP}
`
`ASANO Tetsuya
`Gsaka-shi
`
`Osaka 540-8287 (IF)
`SAKAI Akintire
`Osaka-shi
`
`Gsaka 540-6207 {UP}
`NIGHIG Yusuke
`Osaka-shi
`
`Osaka 540-6207 LIP}
`MIYAZAKI Akinobu
`Gsaka-shi
`
`Osaka 540-8287 (IF)
`HASEGAWA Shinya
`Osaka-shi
`
`Gsaka 540-6207 {UP}
`
`(74)
`
`Representative: Griinecker Patent- und
`Rechtsanwdite
`PariG mbB
`
`Leopohkistrate 4
`80802 Munchen (DE}
`
`
`POOR
`
`(84)
`
`64)
`
`EP3745422Al
`
`SOLID ELECTROLYTE MATERIAL AND BATTERY
`
`(57)
`Provide is a salid electrolyte material represented by.cumposition jommuia List)Xsohy, where Muincudes:
`atigastane kind selected frora fe graup consisting of metelinid: slements and metsl clernedis other than Liand ¥)X is
`atleast one kind selected fronrthe drouy consisting Cl Br and f)O< actbt sepand 6d< 6.
`
`Prrted bydouve, S50} PARIS (FRE
`
`

`

`EP 3 745 422 At
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`Description
`
`BACKGROUND
`
`i. Technical Fisid
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`fOO07] The present disclosure relates to-a satid-elecieniyie mateadal and a ballans.
`
`2. Description af the Relea Art
`
`{O002} PaisntLisrature.] discieses an albscid battery using @.sulfide.sold slectralyte.
`fOU03] Non-Patent Literature { discloses ion conductivity ofa hatide sated electrolyte inchrtling inclum and fuorine.
`
`GHATION LIST
`
`Patent Lheratuce
`
`{8604} Patent Literaiura 1 dspanese Patent Apptication Publication No. Mi1- 129312
`
`Non-Patent Literature
`
`fOU03] Nar-Patert Literature $:'¥. Tomita et. al. Recent Imovations in Chemical Cngineerng, 207%, 10, 12-17
`
`SUMMARY
`
`in the convertionatan, realisation of a sald -electrohte maternal having high heir fon comductividyis desirect.
`IOOO8}
`{007} The sold eiectroiyie matertal according fo ane aspect of tie pragent disclosure is represented by a-compositian
`formida LiYahoseaFg:
`where
`
`Munchidesat least ane kind selected fromthe graus consisting ‘of metsiioid demenis ana metal elements ather than Li
`and Y:
`* ts at least enekind selected from the. qraup consisting Cl Br, ared i
`Ox a
`te
`f< ec; and
`Q<d< 6.
`
`f6888} According he the present dischagure, a sclid electrahte material baving high hiurn fan conductivity cad be
`realized.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`PG009]
`
`a ic o
`FIG. Vi
`t
`Tass-seclional view showing a. schematic canfiquration of a hettery 100-in a second ercbedirment.
`2
`FIG.
`
`FiG..3.is 3 grach shawing an evahiation rasull ahion conductivity by an AC impedarice measurement.
`we 55)
`seB eh athorB®heeli& Q2 oo aaBh&a.aoo&
`190]oeaoeog iasFeet=a ty mySeat
`4
`
`DETAILED DESCRIPTION GF THE EMBCORIMENTS
`
`f0018] Hereinafter, an embodiment of fhe present disclosure wil be described: wih reference fe the drawings.
`
`fFirsbambodimenh
`
`8014] The seltd electratyia matenat in iheirst-embtocdiment is 6 material migreseniad hy the following composition
`formula £1y
`
`LigYpht.XeoF a
`
`Formala (1)
`
`

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`EP 3 745 422 At
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`where Mincludes atieast one af metaiion elements and melal elameants offer than Li dithtam) and VY {ytiiam)
`
`{O42} Xisore.ocmare kinds af elements selected fromthe qraup consisting of Ciichiodne), Br fbroraine), andi tigdine}.
`FOU 33.
`in addition. the sotkt eleciraivte paatenal in the first embodiment satishies the fallowing conditions:
`
`O< a,
`0-0
`Os coand
`Ged <8.
`
`{0074} According te the above configuration,.a salid sheciralytematerial having high Wihnen ion condactivty can be
`realized.ia otherwords, fluorine ts imfroduced ints ihe halitie solid’electrolyte maternal io wapraye alecirochemical stabinty,
`and high hthipejoan-canductvily can be maintained. On the other hand, in the canfiguration of Non-Patent Literakwe 4,
`the tihnum ion cornducihity is remarkaidy kwered by the mirachictod of fluorine.
`POTS] i addiion, according tothe aonave sonfguration, by using the. said electraiyie material of the first erabodiment,
`arnal-solid secondary batlery which does nalincude sulfur can be-realized.
`la other words, fhe salid electrolyte material
`af ihe first embadinient dues not-have a configuration Gor exanpie, the configuration of Patent Lieratve 1) in whieh
`hydrogen sulicie is generated when exposed ig the air As aracsdih analt-spolid secandary hatiery which das nal generate
`hydrogen sulfide and is excellant im safety.can be realized.
`{O16} The term “retaticid eiement™ refers to DSi, Ge, As Sb, and Te.
`{A017} The term “metal element’ refers io-al slements included in Groujs 7} 40 12 af-the perindic fable axceant for
`hydrogen. and all ciemenis inchided in Groups 13 to 16 of the peridic table except for alf the metaliont elements, CN,
`FOO. 8, and Se.
`in other svonls, the mate lament beccmes. a. oater: whad theometel element fans aq inomanic
`campound with & halogen.
`{8038} M mey be one oc more Kinds. of etermenis selected fram the group consisting of Mg, Ca, Sr, Ra, Zn, So, Ab Gat,
`Bi Zr, HTT, Sn, Ta, and Nb.
`[8678] According tothe above configaration, ihe ian conductivityof the solid clectnaiyie matenal. can be furtherjmproved.
`[6G30}
`in the camposiion focmala (7)
`
`os &
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`
`aG
`
`a@+3b + me = G may be satieied.
`{G021} Here, mis avaiades of M, and im=O fe= Cc.
`{O022] Accardingioihe above configuration, the jon conducinity ofthe solid electraiyte maienat oun he further improved.
`[6033}
`in the composition focmaia (Thc = may be satisfied
`[OG34}
`iInihscase, O94 b< 138 may be satisted.
`{0025} Acconlingtothe above configuration, heian conductivity ofthe sulid electrolyte materialcan be further improved.
`{0026}.
`if the cofmpasition fermida it}, 8 4c may te satistied.
`[O027]
`inthis case, Minay tbe one. or more kinds of elemenis selectedframihe group cansisting ofCa, Sr, Bis, Zand Af,
`{G028}9Accarcdingiathe above configuration, ineion conductivlyof the solic cleciralyie material can be hirtherimproved.
`fO029} Mimay include Oa. For example, Mmay be Ca.
`PG038}
`bvilic ouse, 8.05 <0 2may be satistied.
`fO031}
`In tiie case OG <ob=< LU7 meybe further satishead.
`[0032] Accordingiothe above canfiguration, the ion conducinity ofthe solid electrolyte material oan he further impnwved.
`70033} M mayitelnde Sr. For esariple, M ray be-Sr.
`
`{0034}
`In this case, (.1S << B.Smay be satisted.
`{R035}
`in thiscase. 2.4 <a3.7 may te further satistied,
`[0038]. Accordingtiothe above configuration, thejan conducivity ofthe sald Hectrolyie malenal can be further improved.
`[6037] Mmayinclude Ba. For example, M rey be Be
`M038}
`intusocase, OTe 240-6 may hesatished.
`(0039]
`inthis case, 1.6= b< 1 may beturther saltisted.
`(8040) Accordingte the above configuration, heion condtuctiviy of the solid slecirohte material can be further improved.
`fOO4d7]
`Mo meay Include Al For example, M ray be Al
`042]
`In ihis case, co 0.1 and b= 0.9 may be safisfied.
`f043} Acourding ta the shove configuration, hie ion tanductivity afte sokdelectrohie maternal canbe further improved.
`[0044] M ciayinclude #6. For example, Muay be 2r
`[O025].
`inthis case, 0.15 2.08 Bo may be satisfied.
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`EP 3 745 422 At
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`fG046} Wiihis case. f.¥ <b <0.85 may be further satisted:
`{0047} According to ihe above confauration, theion condticivityof ihe sohd slentrofyte maisdal canhefurther improved.
`{8048} Fhe scid-dlectralyia material in the first embodimnentimey be. crystatiine or amorphous:
`6048}.
`in adelifion,.a shape of the solid stectrolyte naateral in ihe first enviadiment is nat specifically liniiad, tit may
`be, for ekamole,an-acicular shape, spherical shape, Gr eligtinal sohedcal shape. For example, ihe solid electeniyte
`material in the fist embodiment may be partides, A plurality of the particles are stacked, and then the plurality ofthe
`parigies may bedanmced into-¢ pellet shape or a plate shape by pressunzaion.
`{O0S0]
`For example, if ihe shape of ihe sain electralyte material in the first embodiment is particulate (for exarapte,
`sohericall the madian diameter of the salid elertroite material may be nolless than 0} wm and not moreihan FOO ym.
`{051} Wiihe first embodiment, the median diameter ofthe sold alectroiyte maternal may be not fessthan 0.5 payand
`net pore than 20 pan.
`f60S2] According te the above configuration, ton condustivity canbe further iiproved. in adelition, a betier dispersion
`siete ofthe sald electrolyte material and an active material in the first emiodiment can be farnad.
`{6053}
`inthe fyst-amboaciment, the macian diameter! the solid elactolic matenal may be smaiier than the median
`diameter of the active matenal.
`
`{8054} Accarding to the above configuration, a belter dispersed siate of ihe salid eleciralyte maternal and the active
`material in the firsf embodiment can be fonned.
`
`« Maratactunng method of solid elecirdyfe maternally
`
`fG055} The solid electraiyie meterialin thefratembodinentmay ve manufachwed by the liawina mathad, for axanipie.
`fOUS8] Binary halite raw material powders are prepared so aste provide a blending ratkraf a-target cormpesition. Por
`exerepie LigYBreF y is produced, Libr, ¥Bra, and YFsare prepared ale. molar ratio of approximately 3) 0. BS O27 in
`consideration of a change in composition during a synthesis pracess. ihe Mending natin may be-adiusted in advance 40
`as.to cancel the change. in this way, ihe above-deserhed values. "a", “h" “c" snd “d" can tee aciusted.
`fOGS7} The raw mofenat powders are mixed well, and then, the raw material powders sre mixed and grotind to react
`USING 4 mechanochemical milling method. Subsequently, the reaction sraduct may De sintered ina vactany of inert
`abnospherea.
`{0058} Alernatively the raw maternal powders may be mined well, and then sinferdd in a yacuurn OF in an imert atmes-
`phere. iis preferable thatthe caw material pawders is sintered, far eiample, within arange af TOQ5C tp G50°Cfor ane
`Roun of jorge.
`{0059} Thereby, the solid electrohte material nchuding ihe compostion as descriied above is provided.
`
`(Second embodiment}
`
`{8660} Hereinafter. dhe second embadiment will be described. The description which has been set forth in the sbove-
`described Erstamibadimeniis oniiied as appropriate.
`{O08} The battery in the second embodiment is configured using the sold electrofyfe meterial deseribed in the first
`enibadinent.
`
`fOU62] The battery in the second enihodinient imeiudes a soli] slectroiyie material, a -pasitive electrads, @ negative
`
`electrode, sridan cleatratyleix,ayer.
`fO083} Thee eleniraivtie layer is a layer prayicied hebveen ihe positive siectrode- and the negative electrode.
`{0084} At lgasi one ofthe positive slenirade ihe electrolyte layer, and ihe negative electrode includes the sokd elec
`iraiyte material in the frstembodiment.
`fO065] Accarding to the above configuration, a battery using a-saltd electraiyie matertat having Tigh ithign ion con-
`ductwity can be resized. Thereby, for exams, a change / discharge tharactersticof the battery can Ge. improved.
`{08S} A specific example of the battery in the secand embaciment wil be described below.
`{0067}
`FRG. iby a cross-sectional view showing 4 schematic configuration afa battery NNT in the second embodiment.
`POUSS} The battery 1000 in the second ambadiment comprises a positive electrode 201, anegative slectrade 203. and
`an alectralyis foyer 202.
`{0089] The positive cieciode 301 Inchides positive electrodeactive material particles 204 and sala electrolytepariicias,
`$80.
`
`{8075} The electrolyte layer 202 is dispased behveern the positive clecirade 201 and the negativeelectrode 202.
`fOO7 1} The elactrolyie layer 20? incindes an elactrolyie material Tor exampie, a sald electroivie matenal.
`O72] The negalive slectrade 703. includes negative electrode active material particies 205 and solid electrolyte
`parikges 7G0.
`fO073}] The suid ciectroiyie paricies 108 ate catticias fanned of ihe sattd alectroiyie madecial in the frstembodiment
`oy particles including the solid alectroite matensl in the Trstembodiment as 8 main component
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`fGO74} The positive slecirace 207 includes a matenal having 4 propery of sioting and releasing metalions (for examale,
`Hihium dois}. The gosdive elecitade 20) iciudes, for examole,.a positive eloctrade aclve material (for example, the
`pasilive elecbode active material particles 304)
`fOU7S]
` Exaninies of ihe positive electrode active material include a fihkim-containing transition raetal axe fe...
`LESICGANO.s or LttoO5)a tansiion moti huoride, a polyanionic material, a fuodnated polyanionic mataial a iranmsiticn
`metal suite, a tansijon metal oxyRuaride, a fransitian metal axysuifide ora transition metaboxyniide.
`{O076). The median diameter af the positive electrodeactive material particles 204 ray be nal lass than Qt pm and
`not more than [00 pm.ihe median diameter of the positive electrode active maternal parliddes 204 is jess than O.f pm,
`there js apossibliy ihat a goad dispersionstateof the positive elecirade active matetial particles 204 and sold electralyie
`particles 107 fails fa-be formed jn the positive dlectrdde. As a tasull, the charge / discharge characteristic of the battery
`is deguacded. In addition. if the median dianieter of the positive electrode active material panticies 204 is more than tog
`yeh,urd difusion in the positive electods active material particies. 204 is made stow. As a hesuit, Bh may be difficult
`ta apersie tha batlery-al « high output.
`{G077} The median diameter of ihe positiveelectrode active maternal particles. 204 may be larger then the median
`diameter of the sald eleniroivte particles 100, Thereby, a qood dispersion state-of-the positive alectiode active material
`particle 204 and the solid slectrobte particies HG can be formed.
`fOO7R] With regard to & wsume ratio “vw: TB0-- v° between ine positive siectrade active material particles 204 and the
`aad sleciraiyie parligies 100: inchded ih ite gostive slectrade 204-30 <v 3 95 may be salisied: Hw <30: imay be
`dificull ic secure a sufficient energy densityof the battery. in addition, Ty > G5, i may be diicullte operate at high output.
`{UO79} The thickness of the postive electrode 2O7 may be nol fess han Hi pm.and not more Bian SOO quant. 1 the
`thickness of the posilive slectiode is less than 70 yh, i may fe dWficul ki secure a subficient enargy density of the
`hatlery. W the iiickness of the posilive slectrade is more ihan SOG pnt, i may be dificult te operate af a high adtout
`{0080} The electrolyte igyer 30215 « layer inchiding. an alectrohie material, The alectrohie material is, for exampie,a
`solid electratie miatenal. in ather wards, the electrolyte layer 202 may be a soticl electrolyte jsyer.
`{8081} The slecirolyte layer 202 may include ihesolid elactralyle material inthe irsiernbodiment as a main component,
`Incather words, ihe clectrolyte layer 702 may miclude the sotiel stecirahytematenat in the fret-emibacdiment, for exarapte.
`aba weight ratio af not fess than.o0% (nef less Than 50% by weight with respect to the entire electrolyte layer 202
`f0082] Accordirig tc the above configuration,the charges discharge characterisiic of the battery can be further improved.
`{O83}
`in addition, fhe electrofyte [ayer 202 may include the sald slectratyte nvatenal in the first embodiment, for
`example, al aweightraticof nal less thar 70% inotiess than 70% by weight} with fescect io. ihe entire aiectralyie layer 202.
`foue4] Accordingio the above configuration, the charge) discharge charactarisiic of the battery can be further improved,
`[G085}
` Theelestrohie iaver 202 may include the slid slectrohdte maistialin the frst ambnadimentas the main coripanent
`iveraoy, anc ihe electrolyte layer 202 may furtier include ineviatle impuntios. The electrolyte layer 202 may inchide the
`sisting materials used jor the synthesis of the acid electralyte material in the first ambadiment. The elactohtelayer
`282 may inchuide by-products or decumpositien products generated when the saticd-efectratyte material in the first-em-
`bodinentis synthesized.
`fO086}
`in addition, the clecinatyia Mayer 20S may include the solid electrolyte. material in the first amhocimant, for
`example ata weight ratio of (08% (1005s by weight with respect in the entire sale eleciralyte iayer 202) except far the
`Mawiaiie IpuTHies
`fOue7T] Accordingio the above configuration, the charge! discharge charactarisic of the battery can be further improved.
`{G088} As described above, the elatiralyieiayer 202 may be composed only of the solid slecbohte material in the fest
`eniGodinient.
`
`(UOR9} Avernatively, the electrolyte lnyer S02 may be composed only ofa soikt electrolyte matena] different from ihe
`solid glectralyie matenal inthe fust embodunent. As the solid electraivie metenal differant fram the salid elactralyte
`matorad in fhe first ernbodimeant, for example, LisMigM,, LipFexy, LAL Gainixy, LifAl Gadning, ar LELKOF. (4, Br, 1}
`Tay Bese.
`{090} The sold clectralyte layer may simuttanecusiy include the sohd electroiie matenal in the firsfambadirnent and
`
`ihesolid electioiyie matanal different from the solid electrolyte materi’ in the first embodiment, At this time. both may
`he dispersed untormiy. A layer formed of ihe solid slectrotyte material in the firstembodinent and « fayertorned of the
`said electrolyte matenat diferent fom the salid plectrohte matenal wr the firsbembadiment may be sequentially arranges
`im a stacking diection of the battery.
`{0094] The thickness of the sufid slectrofte Jayer may be not tess than d gam and mot more than 1,000 gm. ff the
`thickness of ihe schd electrotyie layeri less. than tar, the possibility thal the positive eleactrade 207 and the nedative
`electrode 203 are shortciouited Increases. In addition, if the Huckness of the sold slectraiyie layer is mare than 1,000
`pr dt may be dificult te operateat a-high output
`{0092} The negative electrade 70S includes a matenal having a property of storing and releasing metal jons (for
`example, Wim. ions}. The negative etectmde 203 inches. fer exemple, a negative electrade active material {ior
`exanipic, the negative siectrade active matenal particies 205}
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`A metal mdierial, a carbon maternal an axide, a rinde, atin carmpound, or a silicon camoound may be used
`fG093}
`as ihe. degative electrode active maternal, The metal material may be a single metel. Alematively, the metal material
`may bean aiioy. Examples ofttie metal niaterial inciuds iithiummetel andalihhen alioy. Examples of the carbon meterial
`include natural graphiie, coke, graphitizet carbon, carbon fiber, sohencal carbon, ariticrd granhite,.and amorphous
`carhon..Fram. the viewpoint of capacity density, siican (50, tn sn}, 8 sticon conipound, or & tie cornipaund may be
`preferably used. f a negative clectrode active raterial having & low average reaction vollage ts used, the effect of
`sugpressing elactrolysis by ihe solid etectroyie matertal sy ihe first embadinentis better axhibted.
`{6084} The maodian diameter uf ie neualive electrode active matenal particles 205 may be not less than.1am and
`rrot mare then JOO pm. ithe median diameter of the negative clectrade active maternal particies 205 is |
`gin, there isg possibly that a good dispersian state of ihe negative electrode actwe matenal garficles 205 and the said
`electrolyte particles TOG falls io be Famed in the negabve electrode. Thersty, the. charge / discharge. characteristic af
`the battery isjowered. Onfhe other hand, the median diameter ‘of ihe negative electrade ative material partinies 205
`issmoare than 10 pra, lithiuen difiision in the negative electrade active malenal parivies 205 is made slow. As @ resall,
`it may be diffeull to apersie the batlery.ai a high cuipia.
`fO0SS] The mecian diameter of the negative electrode active matenal particles S05 may be larger than the median
`diemeier of the sold slaciraiyte particles 100. Therehy, a goed dispersion state of the negailve electrade active material
`particles 205 and the solid electroiyie particles 100 can be formed.
`
`
`fO086] Wiihtregant io a volume rata “vy : JDM)- v" between the negaliveclectrade active snaterial particies 305 and the
`solid elactrotyte particles 100 included in the negative electode 203, 3} <v < 94 may be satisfied ify < 30, timay be
`difficull ic secure. asufficient energy densityof the battery. dr additionWy > 5, i may be aiicullie operate at high output.
`{0097}. The thicknass of the negative electrode 703 may he notiess than Td yam ard nat more than 500 um. if the
`inickness of the negative eiecinade is fess than 4wm, f may be difficult fo secure a sufficient energy density of the
`battery. In additien, tthe thickness of the negaiive elacirade is more tien 5G pm. tmay be difficull fo operate at a high
`outout.
`{8098} At lgast one of ihe pasilive electrade 201, the electralvie inyecZO2, and he negative ciectinds 203 may Incluse
`a siliide sat! aiectrolyte or an oxiie salioteciraiyte for the purpose of enhancing ion conduchyvity, chemical stabiity,
`of aleefrocheriinal
`stebilty. AS fhe sulfide
`solid. dlectmtvie, LiGh-Py8, LigS-SiS5, LindBySs, LigS-Ged,,
`Lig-asiGeyonP pate, OF LinGePoSy> may be used. As the oxide sold electrolyte, a NASHOON solid plectrale such as
`LITS(POy), and its slement subshtution products, @ (LalihiG, perovskite solid electrolyte, a LISICON solid electrolyte
`such as Liy/niae,O,, LigSiOy, GeO, and their element substitution products, @ Gamet solid electraiyie Such as
`LipbagdipOy, and ts clement substitution products, Li,N and iis H substitution products and LPO, and ita N subsitision
`products vaay be used.
`fO0898}] Atleastane of ie cosive eiactrade 277, ihe slectrolyte layer 202, andthe negative alectrade 203 ray Include
`ararganic polymersatd electrolyte for the pursose of ncreasing log conductivity. As the organt: polymer solid chactratytie,
`for-examme, a carmpouiund of & polymer compound! and a ithium salt may Ge diced. The polymer compound may fave
`an athydene oxide sinictuce. Due tothe aihylene oxida siruchivaa lage aroun ofithiam sal may be included ta further
`increase the ion canductyiy. As tie lithigm self, LPF. LIB, LISbr,. LiAsr5, USOgCF, LING OSCFaby, LIN(SOaUSFsho,
`UN(SO,CF.NSOn0Fe) or LOiSOoOFale may beused As the filium salt, ore Kind of ithium sail selected fram these
`may b6 used alone. Aliematively, a mixture of two or more Kites of dintam salts selected From these may be tisead as
`the Hthiura salt:
`
`[6700] Aljeast ane of the positive electrode 204 | iheelectrolyte layer 202, and the negative slectrade 203 may inchide
`& RO-equeous glectrobte solution, adel alectruite, or ar joo Hquid far the purpose of facitaling the exchange of
`Hin bonsand aproving the oufpul characteristic of the batiery.
`fe1O1}] The noreaqueous electrolyte solution ieludes @ son-agueeus solvent and a ithiuemsell which hes been dis-
`adivedd i fhe. non-aquesus solvent As tie non-aqueous solvent a cyclic carbonate selventa chain carbanate solvent,
`a cyctic ether solvent, a chain etter sciveni, a eyclic ester solvent, achain aster salvent ors fuarine. solvent may be
`used, Exaripies ofthe cyche carbonate salven include ethylene carbonate, propylene carbonate, and butylene carbonate.
`Examples of the chain carbonate solvent include dimethyl carbonate. ethytinethyt catbansie, and diethyl carbonate.
`Exampies-otihe cyoic ether solvent include tetrahydrofuran, | 4-dioxane, and ISatioxolane Examples of the chain
`ether solvent include 1,2-dimethaxyethane and 12-clelhoxyethene. Examptes af: iheccyclic aster solvent inchide ye
`butyrofactane. Exaraptes of the chain ester safvent include methy acetate. Examples of the Buarine solvent: include
`ihearaattwians carbonate, riathy! fuerograpionate, fuombenreade, huameihy! methy! carbanais. and fuoradimethyiene
`carbonate. As the non-aqueous scivent, one kind pf non-aqueous solvent selected from these may be-used alane.
`Atfematively, & cambination of lwo or more kinds of non-aquesus solvents selacted fram these may be ised as the nore
`adenus solvent: Tha nenaquacns stactralyte salution may inciude af least ode kind of fucride solvent selected Tram
`the graup consisting of fuarceihyiens carbonate, methyl fuoropropionate firobenzene, flucroeihy! methyl carbonate,
`and fluoradimethylane carbonate. As the itum sali, LiPF,, LAF, LIBDF,s, DAs, LiSOgOFs, LIN(SOsCFa)y.
`UNS G.CoF ely, LINISOSCFaANSOACFal, or LICQSO.CE sa}, may be used. As the fhium sail, are kind of Hhtum sail
`
`

`

`EP 3 745 422 At
`
`selected framthese may be used sione, Atematvely. a nuture of wo or more kinds of ihium salts selected fram these
`may be used as the hur seal. The ooncaniration of the fihiin salt ts. ior example within the range af 05 to Falter.
`0183} As the gel-electralyte. a palymer malarial including the nan-aqueaus Slectolte sciution car beused. As the
`pohmier matenal, palyethyiens.axie. polyacrianiirie, polyvinylidene france. pafymethyl methacniats, or a polymer
`Raving an ethyviens cunte bond may Be used.
`FOI93} The cation forming the jonic laid may be:
`
`an aliphatic chain quatemary salt such as tetraaikylaramaniiumof teiraalkyiohoasphodion,
`an. alighatic cycie ammoniin such as pyraliginium. momhalinigm, imktazaiinkim, tetrahydrapyamidinkun, pioer-
`aminiim, of ciperilinian, or
`a nifpogen-cantaining heleranyclic aronratic cation such as gyrdinitum oar imidazolium.
`
`ta
`
`23
`
`23
`
`{G04} The anion forming theranic quid may be Pro BF. SuPys, Aste, SOsCF,, NIGO.CFai, MSO,CAFche,
`NiSQsCFsi SOCFay, or CHSOOCK 3}_". The tonic liquid may include a ihesalt.
`POTS] Atleastane of tite cosive eiactrade 277, ine alectrolyte layer 202, andthe negative alectrade 203 ray Indude
`@ binder for ihe purpose of improving the adhesion between. the particles. The binder js used to Improve the binding
`property of the material forming ihe clectrace: Examples of ihe binder inclide palyvinyidensRuorde, pohfetrafiuoragtit.
`yiene, polyeihylane, palypronyesa, aramid gesin, polyamide, palyinide,. solvamidsimide, palyacoianibie, palyacrylic
`acid, methy! polyacryiate ester ethyl pabyachylate esher hexyl polyacrylate ester, polymetiiacryviic acid, methyy pohwneth-
`
` wider of hyo or mare kinds of matertais selected from fetraiuoroeihylene, hexafuarcethylene, hexaiitiorograpyi-
`
`ene, verfhrorcalky! vinyl eiher, viwilidene Ruoride, chlorotdfuergethyvene, ethylene, propylene, pentaliuerapropyiene,
`fiuerame#thy ving wiher, aormlic acid, and hexadiene may be used in addition, hwo or mare kinds of selected front these
`may be mixed and used as the binder.
`IO4O8}
`inadditian, atleast ome ofthe pasifive ciectrode 207 and the negative electrode 20S may inciide.aconductive
`agent aa specesaarny.
`f3O7T} The conductive agent is ased tc lowerelectrode resimance. Examples ofthe conduelive agent inchide graphiie
`such as natural graphite of artificial graphiie: carbon black such as acetylene black or ketler black: a conductive fiber
`such as sc oarborr liber Gra metal fiber, carbon Ruoride: amelal powder such as shiminumicd conductive whisker such
`ay zinc.uxide of potassiim fifanate: a conductive métal oxide such as tfaniuim oxide: or a conductive pohwner canmpound
`such as polyandne, polypyirele, ar pohaiiaphene. Cost reduction canbe achieved by using a carban conducive agent
`as he conductive agent.
`{8193] An exariple of the shape ci the battery in the third ambediment may be-a coin, a oivider, a prisra, a sheet a
`hufion. a fiat type, or a stacking structure.
`
`EXAMPLES
`
`aG
`
`0109} Hereinahier, details of the present dischasure wi be descabed with reference te diventive examples and cam-
`parafive example.
`
`xinventive axaniple 7s
`
`fPraduction.af Solid Elaciraiyte Maternal]
`
`In an argon almosphere with 4 dewpoint of -GO°C of less, raw material powders Libr, YOry, arid ¥Fs were
`fOF190}
`prepared ata molarratio OF LIN OYBry oYFs = 320.83 O17. These were ground and mixed ina. mortar. Subsequently,
`militig orocessing was performed at 30 momfor 2 haurs. using a planetary hall mat
`POtd4]. Thus, a poweler of the sulid electrafyte material of the wrventive exampic T represented by the camposition
`formula of LGYSreF, was provided.
`
`[Evaluation of loy Conductivity}
`
`FIG. 2 is a schematic diagram Showing an-evalation methad of ion conductivity,
`jO112]
`0713] A prissure-matding die 200 is. composedof atrame 301 fomned of an electronivally insulating gplycarbonate,
`and arcupper puch gart 302 ands lower punch part 302, both of which are formed of electron conductive staintess steel.
`fOtt4]
`fon comfuctivily was evahicied by the fotiowing method using the configuraiion shows in FRG. 2.
`iCf75]
`inactatosphere with a dew point of 30°C of lower, the insxie of the prassuremolding die 300 was Med
`
`

`

`EP 3 745 422 At
`
`with the pawderof fhe solid clectrolyle material. of the inveritive example f, and was uniaxially pressed at 400 MPa to
`produce a Condicviy measurement tel of ihe inventive example 4
`[0116]
`in a pressurized siste, lead wires were routed frord. the upper pudch part 303 and the jawer punch pari302
`and were connected toa potentiostal (Prineston Apphed Research VersaSTAyl4} aquipned with & frequency respanse
`anatrer The ion conductvily at room fempersture was measured by an electrochemical sapedance measurement
`method.
`
`[O47] FG. Sshows 6 Cole-Cole diagrarn of the resulls of the imoecdence measurement,
`fOt3R]
`in FiGc. 3 areafvaelueof the impedanceat the measurement point larrow jn FMS. 3} haying the smaiiest absatute
`vahie of the phaseof the compleximpedance was deemedte be the resistance value fot ihe jon candaction.af the sold
`slectraiyie of the inventive example 4.
`{@t99} The joa conductiviy was calculatesfram the following formula. {7} using the resistence value of the elactralyie.
`
`o= (Rse x Si)(2)
`
`where o iS lan canductivily, & is an. electncivie area dinner diameter of fhe Fame 307 in. FRG. 2), Auis the resistance value
`ofthe solid electrolyte inthe above-mentioned impedance measurement, and tis.a thickness of the electrobte (in Fic.
`2 the thickness of the compressed body ofthe pluralily-of te solid slertrafyte partichas. 105).
`fe120}) Thejon canductivily ai the sole elacirciyte matenalof the inventive example | measured al 22°C was 2.58.
`104 Sion.
`
`einverdive examines 2 if 63 #
`
`iO%21} Hersingfer, synthesis and evaluation methods of LipYyhl,<g.af y will be described.
`
`fProduction of Said Electrotyie Material}
`
`inthe inventive exanipies 216 83) raw raatenal powders were pregared in.a Glove bax mainigined in a dry tow
`[0422}
`Oxygen aimasphere having a déw point of -90°0 of lower and an axygen vale ofS opr or lower,
`[G723}
`in the inventive examples 2 io 4, aw maternal powders LIBr, YEr3. and YF, were prepared ate the malar ratin
`OFLIBT YGrg. YFg =a 003 - dS OW.
`FOt248}
`in the inventive exarniple 4, rawmaterial powders LET, YCl,y. and YFa were prepasted al a molar ratio oPLICY:
`Wigs YE3=
`3:60.93 70.87.
`{6425}
`intthe inventiveexample 9, raw matertal powders Lil and YFg wer prepared al a malar ratioof LH YFa= ht
`
`os &
`
`ta
`
`ag
`
`aG
`
`inthe inventive example 7, raw materiel powders Li, Lidr, YBr, and VF. were prepared sta molarratie of LH
`{G426]
`LIBr 2 ¥ Bra ¥ Fs = 0.5 2225 033-2 OF,
`{0427}
`in the inveriive examole 4, raw material paweers LH Libr, and YF. were prepared ata. molarratic of LH LIB:
`¥Fa = 2.
`{0728}
`inthe inventive exarnples 9 to. J 7, rawmaterial powcters UiLIB, YBr., and VF, were prepared ala malar ratio
`OFLEO LIBr LY BErs YFgs 20 a- 200 - Wao.
`fO%29}
`In the inventive exerapepies2S idand 19, raw material powders bi, LIE Yrs, and YF, were prepared ala mohar
`fO430].Inthe invenme exanywe 20, ravi maternal powders Lil, VEra, and YFrawere prepared af @ molarratio ofLN:
`ratio oF £0 LEB YBr,0 YFa=23.5 0a- MS 00+ d/0 a3.
`POPS} ethe snventhve example 21, raw material po
`ns Libr, Lich YClh and YFawere prepared at a nvolar rate 2
`
`Y¥Brq.¥Fq = 210.5 00.5.
`
`
`LIBR LEM Wig: YFgo 209 00330 (Ley.
`[6132]
`in thainventive example 22, raw material powders Libr, ¥Cl,and YF.3 Were preparedat a malar rate. of Likr
`¥Cig( ¥Fq= 310.80 OA.
`P0133}
`in he inventive example 27. rawmaterial pawtiers Li, LECL Will, and YF. were prepared at a malar ratio at
`LHL: YOR OYFa 5 Sr bo Oey.
`[C134]
`in the Inventive example 24, raw maieral powders Li, LIGr YEr,, YF, and CaBr, were prepared ad a sidlar
`retiy of Libs Life YBe, (YF, 7 Cabs, = 0.5.90 GAS 0.68 00.58.
`{0195}
`in the invect