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`EP 3736 831 Al
`
`(12)
`
`EUROPEAN PATENT APPLICATION
`published in accordance with Art. 15344) EPC
`
`(433
`
`Date of publication:
`T4:44.2020 Bulletin 2020/46
`
`Agplicdiiod number 18898736.6
`
`Date. of Ming: 13.14.2048
`
`(84)
`
`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:
`BSA ME
`
`Resignatad Vatdation States:
`KH MA MO TN
`
`Priory: OQ5.04.2012 JP 2078000429
`
`Apticant Panasonic Intellectual Property
`Management Ca., Lid.
`Osaka-shi, Osaka $40-6207 {JP}
`
`inventors:
`SAKAI Akthira
`
`Osaka-shi, Osaka 640-8267 iIP}
`
`io
`
`net
`
`ECL:
`HOTB 1/06 OROD
`COIG 27/pg BOD
`HOM 16,059 (208007)
`
`core 2609 FOF
`HOIM 462 CO60U
`HOIM 140862 20ST
`
`international application number:
`PCTAP201 R041 898
`
`}
`
`infemational publication numbec
`WO 2019495321 (14.07.2019 Gazette 2079/28}
`
`ASANO, Tetsuya
`Osaka-chi, Osaka 540-8207 LIP}
`SAKAIDA Masashi
`
`Osaka-shi, Osaka S$40-6207 {IP}
`NISHIO Yusuke
`
`Osaka-shi, Osaka 540-8267 LIP}
`MIYAZAKI Akinabu
`
`Osaka-shi, Osaka 540-9207 {JP}
`HASEGAWA Shinya
`Osaka-shi, Osaka 540-6287 {37}
`
`(74)
`
`Representative: Griinecker Patent- und
`Rechisanwdaite
`PartG mba
`
`Leopokistraie 4
`80802 Munchen (D6&}
`
`
`
`ibd)
`
`SOLID ELECTROLYTE MATERIAL AND BATTERY
`
`ibf}
`
`Provided is a solid eiecioniyie material represented by the folowing compasitim formula tf}
`
`LiggeeVges.aMlaClgypBQh,
`
`Fonte (1)
`
`where
`
`M is. one or niore kinds of elaments selected frarn ine group cunsmiting ef Zr Hfoand Tr
`fe gx oy
`Ox ach sd:
`fh<ogg- B8-ak
`Bef + $a}
`SK 4G,
`@<y¥ <6. and
`xt ypse
`
`Prrted bydouve, S50} PARIS (FRE
`
`(Cont. next page}
`
`EP3736831Al
`
`

`

`EP 3 736 837 At
`
`FIG. 1
`
`

`

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`23
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`EP 3 735 837 At
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`Description
`
`BACKGROUND:
`
`i. Technical Fisid
`
`fOO07] The present disclosurerelatesto-a satid-elecieniyie mateadal and a ballans.
`
`2: Description af the Relatad An
`
`{O002} PaisntLisrature.] discieses an albscid battery using e.sulfide.solid slectralyte,
`{6003] Nor-patent Literature 3 discloses Ligytig.
`{6004} Non-patent Literature 2 discloses LL,YBY,.
`
`CHATION LEST
`
`Patent Literature
`
`{0005} Patent Litersture f: Japanese Patent Appication Puivication Na. ZOTI-T283 To
`
`Noa-Fatent Literature
`
`(one)
`
`Non-patent Literature 1:2. Anorg. Alo. Chem: 623 (1887), 16
`Non-patent Lierature 2: 4 Anerg. All. Cheny. 623 (1897), 1352-32
`
`SUMMARY
`
`f0007}
`
`if theprior art, réstization of a sataBe eeu maisial havexy high hua ion canductiviy is desired .
`
`fOUSB] The solkislectroivte material in one aspect of ihe present disclosureisrepresented by the fokowing composition
`formida £4}
`
`Lis.asa¥ gpaMlaCkkyBr,
`
`Formula C1}
`
`where
`
`ii is ane. or mare kinds of slemenis selected from the graug cansisting of 24, HY, and Th,
`-P<eed
`OsaTe
`
`hoy +8-
`
`U<43 - 3S -a
`
`
`fO09} According to the praesent dischosure, a salid alectrolyte-maferial having high lithiwn ion conductivity can. be
`Feahzed.
`
`BRIEF DESCRIFTIGON OF THE DRAWINGS
`
`F009)
`
`FIG. t isa oross-sectianal view showing a schematic configuration of a hatiery in a secuncd.embadiment:
`FIG. 2 is aschermatic diegrad dustaling an evaluation method of ianic conducthwty.
`FRG. Sis -ag-graoh showing an evaluation result af the ionic conductivity by AC ammpedance measurement.
`FIG. 4 is 2 graph showing an inifiat dischame characteristic.
`
`

`

`DETARED DESCRIPTION OF THE EMBODIMENTS
`
`EP 3 736 837 Al
`
`{ANA} Hereinater, embodiments af ihe cresent-discinsure will be described with reference ta the drawings.
`
`iFirst embodiment}
`
`fOO42] The sciid-eleciratyia maianal in the fest ernbadirnedtis represented ny the follawing composition foameala 3}
`
`os &
`
`where
`
`LiggseVyisalaClspyBGk
`
`Formule (7)
`
`AV is une ar more kiruds of elements selected from the graus consisting of Zr, AF and Th
`
`[6073] Furthernore.-1<$= 7 G<@<45 G9(9-38-ay aea +§-83 O2x S86O< y 68, ad txt y5<6are satisfied.
`[60714]>Accerding io the nbove canfigurstion, a halidesalt elactolyte maternal having high fitham ian cancueliviy can
`ta
`be realized.
`
`ag
`
`aG
`
`{0045}
`in addition, according in the above configuration, an all-solig secandarybaltary excellentie charge‘dischanye
`sharacteristic can be realized by using the solic alectrabyte maternal of the twat ermbadimerd. in addticn, By using the
`ngid slectaivte snaterial of the first eribodimrent an allsotid secondary battery which does nat inchice sulfar can be
`realized. In ather words, d exposed ic the atmasphers, the solid electralyie matenal of thefirst embodiment dows not
`have. a comiguration Gor éxamnpie, the confiquration of Patent Literature 1} in which hydrogen sulfite is generated, As
`aresud, on ait-sciid secondarybattery which does cotqenerate hydrogensulfite and is axcellentin safety pan be realized.
`fOO7B] The solid slectrolyte matenal in the fret embadiment maysatisfy 0.4 £a = 6.9 in the abeve composition formula
`ed.
`OTF] Accurding fo the above configuration, a-solht electroiyie maternal faving higher ithiure jon conductivity can be
`resized.
`
`fO07R] Thesolic electrohts material in the firs{ embodiment may salishy 2.3 <a < 0.7 i the camposition fornauis (1).
`[6879] According to the above canfiquraticn, a sclid ciactraiyie matedal having higher Hhigra ba condustivey can be
`realized.
`
`{0020} The solid clectrofyte materialin ihe first embodiment maysatisfy 1) 4940.4 grthe above congiosition formula
`fFR
`fOU27] According to ihe above configunaion, a sold electralvie material having higher lithium jan conductivity cad be
`realized.
`
`f0022] The sold electroiyie material in the first embodiment may satiety 0.2 =.05 0.2 in the above canmosiion jormula
`OF.
`fOG23} According to the above. configuration, & solid elactrabyteraaterial having higher {ihhimion conducinaty can be
`realized.
`
`[0634} The solid electroivie matermlin the ficst embodiment may satiety -0.) © 3.4 0-4 inthe abave campositiog formals
`(th
`{8025} According tc the above configuration. a solic slectrohte material having higher Hihkim ion conductivity cart be
`realized.
`
`
`{G026}] Thesolid electrohte maternal mthe first embodinent may becrystalline ar amarghaus.
`P0277]
`hradcdifian, ashape ofthe solid slectrahytematenal inthe first emsbocimentis not specifically limited, for exanrole
`may be an acicular shape, a spherical shape. ofan eliipical spherical shape. For example, the solid sleciraiyte matenal
`in thefirstamoodiment may be parcicies. ln addition, the soll electraiyie matedal in thefirst ershodimmedt may be forrnad
`inte & pefiet shane ora niate shape by presstnzafion affer stacking a pluraliiy of partictes.
`(0028}
`For example df ihe shane of the satid eleciraivie material in the first embadunenl is particulate (for exanrpte,
`spherical), the median diameter thereof may be not jess Iman O44 pm and not more than MO pm.
`{0029}
`if thefrst emberdimnent the median diameter may be notlese than tS pr and not mare than 10 jam.
`POU3O] Accardingits ihe above configuration, ionic canductivity ean be improved more. in additions hetlar dispersion
`sigte of the salid elaciraiyle matenal in the firsbembadiment and anwelive material can. be fomned.
`{0034}
`Inthe first embodiment, the-solid electrolyte maternal raay be smater than the raecian diameter of the active
`mMaieriat.
`
`{8032} According in the above configuration, a setler dppersion simte of the solid electmiyie metenal in ihe firsi
`embodiment and ihe active maternal can be formed,
`
`<Manufactiong metioad of Solktelectrahte matenakl
`
`[0033]. The solid electroiyie material in thefirst embodiment maybe manufactured hythe folowing methad, for example.
`
`

`

`EP 3 736 837 At
`
`fGO34} Binary halide raw material powders are prepared so as to have.a blending ratio ofa target composition. For
`example f LipsVasé¥ygCle is produced, LICL YCly, and ZrO, ara prepared ina molar rata af about 2ho 05. tn
`
`considerdiion ofthe change in composition during a synthesis process, ihe ending ratia may be adjusted in advance
`80 a5 to cancel the change. The above-meritioned values "6", "a", “x*. and “y’ can be aciiusted by adhusting the raw
`rateriais, Ihe blending fatio, and tha synthesis orocess.
`fG035}. Aer ming the mw maternal powders well, fhe raw rasterial powders are mixed and ground using armechan-
`ochernioal milling methodie react. Then, the reaction product raey be sintered in a vacuum or in-an inact almesohere.
`[O38] Alternatively, fhe raw maternal powders may be mixed well, and:then sintered in. a vacutun oFan jnen aimos-
`chere. i is desirable thet thesintering is performed for-ore hour or longer within a range of TENE °C. to 350 °C.
`MOI7} Thereby, the sald electrolyie material mciuding tie composition as desorbed above is provided,
`
`Second anibodinierd)
`
`{6038} Haersinefter, the second embodiment will he descdbead. The descriptierwhich has bean sel forth in ihe above-
`described firsbemboduneni is ondited appropriately.
`{8039} The wettery in the second ernbadiient is configured using ihe sold eleciraiyie maternal deseribed in the. firsi
`embodiment
`
`[6040] The battery inthe secand embadiment comprises a positive aectroda, a negative elecirade, and. an electralyie
`hye
`{0041} The eleciraite layer iss layer provried bebveen the positive electrode and ihe neyative efactrode.
`f
`fG042} Atleast one of
`the positive electrode, the ealectroite layer, and the negative electrode iidisdes the sald eisc-
`iraiyte maternal in the first embodiment.
`{6043} Accerding lothe stove canfgurstion, the chargetischange ‘characteristic af ihe battery can be improved.
`{0044] A specific exaraple of the battery in the second embodiment will be described below,
`{0045} FIG. is.acrass-sectional viewshowing a schematic canfiquration aia battery 1400in the secamt embodiment.
`IOO48} The battery HiGinthe second amboadiment comprises & positive electrode 701, a negative electratie 2U3, and
`an clectralyie layer 202.
`G87} The positive electrode 207 Includes positive ciectrade acive matetial particles 204 and sols electroate particles
`BS.
`
`o r
`
`$0048} The-clectroiie layer 202 is dispased behveen the positive electrode 201 and the negative dlectrode 392.
`fO0dS] The slectrolyie layer 202 inches an slectroiyie material for exampie, a solid electroite matenat)
`{0050} The negative electrode 203 inchuias negalive electrode active matenal particles 205 and the sotid electrolyte
`particles (OG.
`fG051} The solid cleciratyia particles 10-are padicies each cansisiing of the solkt elactratyie material in the first
`embodiment or particles each including the sold electrabyte material inihefst embodiment as a main commonent.
`[8852] The posiive slectrocde 20) Includes a maternal having a characteristic af Steriag and releasing metafians Gor
`exaripie, Hihaumions). The positive electrode 2017 includes, for axample, pasiive electrade active material (for exampte,
`ihe positive alectrade active maternal particies 204}.
`fG053} As the positive stectrade active material, for axanipie, a ithiam-cantainiig Wansiion metal oxide-fe.q.. LENE
`COADGSOF LiCoD)), a transition metal fluoride a polyanion maternal a fuonnated polyanion material, a transition matal
`suifide, a transition metal axyfuaride 2 ransition mela oxysulficde and 4 Pansition metal oxynitdde can be used.
`fO084] The mechan diameter ofeach of the posdive electrode active material panicies 204 may be nal tess than 0.4
`
`yin and nolmoare han ioo am ff the median diameter of each of the postive electrode active material parlicies 204 is
`net less then G7 pm. the postive electrode active maisdal panicles 204 and the hate solid electrolyte maianal can
`form A good disgersion state in the postive electraie. As result, the charge/discharge charactarishe af the batteryis
`raproved In-addiian, Hihe median diameter afeach of the positive electrade active material particdias 204 ig not more
`than 100 ani, jihium diffusion inthe positive elecirade active maternal panicies 204 is accelersied. As a result, the battery
`can operate ata high cutout.
`POUSH} The median diameter of each of fhe postive slecirace active material parhcies 204 may be jarger than the
`radian diameter of ihe halide solid electraiyie material. Thereby, the favorable dispersion state.of the postive electrade
`active maternal particle 204 and the halide sold electrolyte material can be formed,
`{0056] With regard to & volume ratio °v: 1G0-v" between ihe povitive-slectrode untive paaterial particles 204 and the
`halide solid slectrolyte material iIndluded in the positive ciectrade 201, 30.< y.< 25 may be satisfied. In a case oF 3G sy,
`a sufficient battery energy density can be secured. In addition, fy < GSan operation at a high oulpul can be realized.
`[OST] Phe thickness af ihe pusitive clactrade 207 may benotless than 10 pum ioe not maretan St) am. iter thickness
`of the positive electroce is 10 pnvar more, asufficient battery energy density can be -arsured. in addition, ie thickness
`of the positive electrodeis S08 um ariess, an operation ata high output can be catized.
`POUSR} The clectroivie layer 203 is a laverincinting an electrolyte material, The electratyte matenalis, for oxampie! a
`
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`EP 3 736 837 At
`
`sand electrolyte. matenal lother words, the electrolyte layer 202 may be a sot atectrolvtelayer:
`
`{G058} The sciid-eleciralyie layer may be composed only of the saciid elsetratyie malandal in the first. ambadimant,
`{8060} Avernatively, the solid electrons layarmay be compased only of a-sold slactroltie material different iram the
`snd elactroivte raaterial in the first embodiment. As the solid electraiytie material diferent fram the salid abectrolyte
`maternal inihe first embodiment, forexample, LigM@Xy, LipFer, LAL Ga, NA, LifAl Ga, injk.. of Lemay be. cased
`Here. & includes at least one selected from the qroup consisting of 1, Brand }.
`{O061]. The said slertrofte layer may include simallanecualy the solid alectrohdte material in te frst embodiment and
`thesolid electrofvte maternal different rar the said! electrolyte material in the firstenvbodiment At thistirae, bufh may
`be dispersed uniiormly. Attematively, ihe layer furnad af ihe sold slestrohte material ia the fest eambodiment.andtte
`layer farmed of the solid electrahte materiel diferent frony the sole cleciraiyfe ragtenial in ihe dist embodiment are
`saquentiaily arranged in the stacking direction af ihe tatiery:
`[0062] Thethickness of the solid electrolyte layer may be notiess tran) porand aot more Man 100 pm. ifihe thickness
`ai ihe solid sleciralyie layer is nalless than dpm, the positive electrode 20% and the negative elecirode 203 are easily
`
`separaind in additian, Wf the thickness af the salid electroiyle layer is ned more Than 160. ,0, an operation at a high
`outpuican be realized.
`{0063} The negative slecirode 203 includes a material having a characteristic af storing and releasing rretal ions. (lor
`example, hifium ions}. The negative ctectrode 203 inmcudes, far example, a fegative electrode active nvatenal for
`exariple, negative alectrade aclive material particles. 206).
`{00848} As thonegaite eiectrode active material, a metal material a canion material, an oxkis, a niinde, atin compound,
`OF @ SHICGR cammound can be used. The metal materisi may be asingle mefal. Aflernatively, he metal material may he
`analioy. Examples ofthe metal metenatinchide dihaun mate sind ldhaun athoy. Eoxerniples ofthe carbon matertal inciude
`natural graphite, coke, graphitlized carbon, carbon fiber, sohencal carbon, arifficial graphite, and antorphoaus carton,
`
`From the viewpond af capacity density, sdicon. (9. tin (Sn), aosdican compound, of Sin campound can be used. Ha
`negative siecirade active material having = low average reaction voltage is used, the effect af suppressing electraiysr
`bythe salid electrotyte maternal in the first ernbodimment is better exhibited.
`fOU65} The median diameter of each of the negative siecirade antive material particles 205 may be nobless than dh
`pa and notions than TOG pra. if ite median.diarmieter of cach of the negative aleotode active material parlinies 205
`
`1A Ad Jess thar 0.4 poem, the Negalive slectoade active matenal particies 205 and the said electroiie paricies TOU can
`
`form & goaded dispersity state in the negative elacirade. As a resull, ne chardedischarge characteristic of the batlery
`imoreved. in addition, if the median diameter of aach of the negaiive electra active material particles 205 is nol mare
`than 1660 p,m, the ithiurd diffusion in the negative electrode active material particles 205 ts accelerated, For this reason,
`the batiery can aperaie at a high outpal
`fO086] The mecian diameter ofeach of ihe negative electrode active matenal particles 205 may be farger than the
`
`median diameter of the soldelpctratyle pariiches 100. Asa resull, he javarable dispersian state of the negalive slecirade
`active maferial partici 204 and the halide Solid eleciraivte material can beformed,
`[OOG7} WHA regard io the volume tatie "v 104° af the cagative clectrade active material particles 205-and the -saiki
`electrolyte partidies 100 inchided in the negalive clectrade 203,30 < v < 95 may be. galistied: In a case af 30 = v8
`sufficient battery energy density can be secured_in addition, Hiv < 95, an operation aia high output can te realized.
`{0068}. The thicknass of the negative electrode 7O3 may he notiess than Td yam ard not ier than 500 um. if the
`thickness of tie negefive electrode is not jess Than 7G am, the sufficient battery energy density can be secured. in
`mddiition 4 ie thickness of the positive dlectrode is motmore tan 500 aim, an operation al a high outpid can be realized.
`fO089}] Atleast ane of ite cosive eiactrade 21, ine slectrolyte layer 202, andthe negative alectrade 203 ray Indude
`&@ Sulfide solid diectratyte or an oxide solid electroiyie for the purpose of improving wonte conductivity, chemical slability,
`and sleckocheminal stability. As fhe sulfkle.solid celactralyle, LisbS-PoSs, LinS-SiSe, LipS-BoSs, LigS-GeSo, or
`LiggeGen osPa gata. LiygpGePoS yy can be used. As the axide solid electralyte a NASICONsolid eleciroijle typtied by
`LITiPO4)s and ds elerient substitution, 4 (LabliitiO< peravskite saiht slactolyte, a LISKCON: sald alechohde types
`bY Liga@hGe,Oue ESiGy. of Lieb, and its clement substiulion, a garnet soln electrolyte typified by Liskassr%O 4,
`and tselement substitulion, Ligh and dis H substitution, or Li9pC, and iis N substitution can be used.
`[0070]. Atleastore of ihe posiive electrode 201, the electrofyie layer 262, and the negative ciectrode 205 may inchide
`an organic polymer solid electrolyte for ihe purgose af increasing anc conducinaly. As the organic palymer golkt elec-
`troiyie, for examiie, a compound of a polymer compound and a ithtura salf.can be used. The polymer compound may
`have an ethylene oxide structure. Since the polymer cornpound fas the eifiylene oxide -sinicture, & large amaunt of
`kihium self can be included, and the ionic candactivily can be farther increased. As the Ethiumsalt,UIPP,, LIB, LISDF¢.
`LIASF,, LGACrs LIS OnC Faj>, LINISQCF5h, UINISOACFaMSO40Fgh of LIC(SO,CF4hCan be usedAs the ithium
`salle Nibhimsail selected from these may be used alone. Altemetively, a mixtureof we or more lium Salis selected
`fram these may be usecas the iihdurd sail
`{@OFt] Atleast one of the pasitive efectrame 201, the electmivie inyer 202 -and the negative eiectrade303 may include
`a non-aqueous alectralyte safistion, a.gel.clectrohte, and an ionic iiquid for the purpose of faciittating exchange af thin
`
`

`

`EP 3 736 837 At
`
`1005 afdimproving the oufpul characteristic of the ballery.
`{GO73} The non-aqueous electrohae sohition includes a non-aqueous solvent acd a liivum salt.dissatved in the nen
`aquecis scivent, As the non-aqueous Solvent, a cyclic carbonate solvent, a chat carbonste solvent, a cyclic ether
`solvent a chain eather solvent, a oycie ester solvent, a chain aster solvent or a fluonne saivent can be usedExamples
`af te. cyclin. carbonate Sovent include athylene carbanate, propyiene carionate, and butylene carsonate. Examples of
`the chaincarbonate soiventinchide dineihyi carbonate ethyt meth carbonate and diethy carbonate. Exaninies af the
`cycle einer schvent include tetrahydrafiucaa, | A-dioxane, anid 3-dicaolane. Exampies of the chain ether saivent include
`7 2dimethoxyeihane and tf 2-diethoxyeiiane. Examples of ihe oyche ester sulyent yiclude y-bufyrolactane. Examples
`af the chain aster salventinclude riethyt acetate. Examples of ihe Nucine sobvent include fludmethyiene carbonate.
`methyt fucropropionate, fiuorbenzena, Ruerasthy! methyl carbonate, and fucrodimaathylene carbonate. As tie non-
`Squequy solvent one non-anueans solvent selected fromm these.can be used alone. Alternatively, a combination af bya
`
`OFmore nor-aqueaus salventsselactedfrom hesecan be used as tha non-aqueous saivent, The non-aqueouseee
`fluorprepioniate, fuorcbenzene, fiparoetiy! methyl carbonate, and Nuaradimethylane carbonate. “As the lthiam sail
`
`sGiution say coniain at leastone fluorine solvent selacted fram the group consisting of fuorosthylens carbonate, meihy
`
`LIPE,. UIBF,, LiSbF.sLiksk., LISGSCEs, INGO LDF a5, LIN(SO5CoF ahs, LIN(SO4CE{SOsFg) oF LIC(SO,CFs); can
`be ised. As the iihium sail, ane ithiam sai sedecte:d fram these may be. used aione. Alematively, a mixhure of fava or
`morefifhiumsalts selected fam these may be. usedas the lithiumsalt. The concentration af the ithiun sail is, for example,
`in the range of 6.4 to 2 matter.
`{O73} As the gel sieciralyte. a polymer material including the non-aqueous lectrofvie solulio can be used. As the
`polymer material, pulyetiviene oxide, polyacrlaniinie, poiyvinyikiens Tuoride, polyrmeihy! methacrylate. ora polymer
`Raving an alhyiend oxide Bond may be asad.
`fO074] The cation which forms the tonic Nguict isan ahphatic. chain quaternary Salt such as. telraaikvlammanium or
`tatraalkylphosshonkim, an alichalc cyche arimonkim such as pyrroldinken, marphotinium, imidazainium, telrahydra-
`ByAGHCIN, Giperazinium or piperidiniiun, « nitrager-inchucing heferacymis aromatic caton such as pyridinium of im-
`idasolkim. The anion which forms thejonic liquid is PFBF. SheASF, SOgCFs, N(SO50Fajo, NISOgCsFaby,
`(SOCANSDOaCPayor CisOgFale: Incadditian, the tonic liquid ray contain a [hiunsalt
`[O875} Allisast ape afthe positive electrode 204 ineelectrolyte layer 202 and the negalive slecitode 205 mayinclude
`a binder fine ihe purposeof improving adhesion between the parities. The binderis used to improve the binding fraperty
`of the materalwhich forme the electrode. The. binders inchidie palyvinyiniene Ruotide, poltetraiuarcethyiene, poheth-
`ylene sokropyiene, aramid risinpobamide, colyimide, pohamideinide, polyacitanitnie, golveorylic acid, pobacryitc
`acmetiyt ester, polyacniic acid ethyl ester, pobyacnic acid hexyl ester, pokrymethacryiic acid. palymethacnylic acid
`methyl ester, polymeihacniin. acid eihyLester, palrmethacylc acid hexeslar, polyvinyRaccelate, polyinyiyrrolicone,
`polyether polyetiersulfane, hexafluorupolypropylene sirens huladiarie puiter, or carboxy mettvieeitioss. Thebinder
`inghides.a copolyrier of hwo or mare materials selectedfrom the group consisting af ipirafise cethviede, bexefunrmetihe
`Wene, hexafiioropropylene, gerfluarsalky! vinyl ether, vinyiniene fuoaride, chlorattRuotaethylene, eityiene, cropyiene,
`penisfuoropropylene. flucramethyl vinyl ether, seryticacit. and hexadiana. In addition, bvof mare kinds selected fram
`these may be mixed andaused as a Binder.
`{UO76}
`In addition, at least one of fhe positive slectrade 201 and the nedalive slectrode 203 mayincintea conductive
`agent as necessary.
`fOO77] The conductive agent is used fo lower otectroderesistance Exameoles ofthe conductive agent incknie graphite
`such as natural graphite or artificial graphite, carbon black such as acetylenee Diack or ketjer: black, a conchuctive ber
`
`such as.g carbon hberor a metal fiber, a metal powder such as:carsen Huorde of aluminum, aconductive whisker such
`a8 Fine oxide or potassium tanate, a conductive metal axide such as itantum oxide, ora conducthve polymer compound
`such as.nohaniine, palypyiale, or pobthinghene. in.addittion, cast reduction can be achieved by using carban conductive
`ager a6 the conducive adent
`[O878} Nate that the balferyy inthe secorid embodiment canbe configured as a batierhaving vadeus Shapes such
`a5.q com shape 6 cylindrical shape. a prism shape, a sheet shape, a bufton shape, aha shape,or alaminaled shape.
`
`EXAMPLES
`
`fOO79}] Hereinafter, deisis ofthe present disclosure wi be descnbed with reference fo inventive examples and cord-
`DROVE Oxanigies .
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`ta
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`23
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`<<rnventive exaninie To>
`
`fPraduction of SolidElectotyie Material}
`
`jOU8O}
`
`inan argon aimasphere with a dewpoint af-O0 °C. ar jess raw material powders LiCl, YCl,, and. 2rCl, were
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`EP 3 736 837 Al
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`prepared af a molar ralic. oF LiCr YCig: 4rcly = 20. OF OT These ware ground and mixed in aimortar, Bubsequanily,
`milling processing was performed af G00 mimfor 25 hours.using a planetary ballymil
`{0081} Thus, powder of thesolid eleciratyte material af Ihe Piwenlive exemple 1 represenied bythe cempasitinn
`formula Of Lig o¥np@fg ls was provided.
`{WO82] The content of Li ger unit weight in the whale af the salid electroivie matacal ofthe inventive exampia Twas
`measured by atomic absorption spactromeiy, The content of Y was measured by IOP amission spectrascapy. Fhe Lr
`Yo Zroontent was converted into a molarratio. The ratio of Lk Yo Ar was 3.9 0.9 04 o.which was ihe sameas the ratia
`of the raw material powders
`
`feyaluation, of Lithtum fon Concdustyity}
`
`FHS. 2 is aschermatic diagram sthowmg an evaluation method of ionic conduchvily,
`fOUS3]
`(0084) Thepressure-moling die 300is composed Gfaframe AN formed cian elactranically Insulating polycarbonate,
`ap upper punch part 303 and a lower gunich pan 302, both of which are fonned of electron conduchye stainless steel.
`{8085} Using the combguralion shown in FiG. 2 ihe ionic comiductivity was evaluated by the following method.
`{0086}
`in -adry aimosphere with«.dew gow of 30 0. or jmwer, the Inside of the pressure-maiding die 300 was. Med
`withthe power of the salid electratvic piatertal of he inventive exarinie 7 Gan inventive exarante of the sold eleciralytie
`particle TOG). The pawder was uniexially gressunzed at 400 MPate preduce a canductivily measurement cell of the
`mvenive examine 4.
`{WORF}
`inca. pressurized state, lead wires wererouted fram the upper cunch part 303 and the lower punch part 362.
`connected fo 8 poatentiostet (Princeton Applied Resdarch, VersaSTAT4) equipped with a frequency response analyzer.
`Theionic contushyity af room tenmmerature was measured by am electrochemical mnedance measurement methad.
`{[G088}
` FiG.3 shows a Cole-Cale diagram of the result of the gmpedadce measarement
`FOO89}
`by FiG. 3, the resi yvaine of fhe impedance al ihe measurement point darrow in Fle: 3) having the smatest
`absolute vahie of the phase of the complex impedance was deemedtc be the resistance value for tonic conduction af
`ihe said electrolyte of fhe inventive exanipie tT.
`f6080]
`jonin conduchvily was calculated fram the following formuta (2) using the resistance value of the electroiyie.
`
`og = (Ree » SAY'(2}
`
`where ois the lonic comtucthly, S is the ehactralyte area fininer diameter of the frame Bihioin FRG 2) and Alois the
`resistance yale of the sole siectratyie in the above impedance measurement, fis ie thickriess of the electrohte fin
`FRG. 2- the thickriess of the pressured body of the pluraity af the solid electralyte particles TO}.
`[6087] Thetonic conductivity af the sobd slectolte rmaterial af the inventive exarinie J measured ai 25 °C. was 7.5
`x04 Siem.
`
`[Production of Secondary Battery}
`
`in.an.argon glove box, the solid electrolyte material of fhe inventive example } and LiICSO,, which is an active
`{0092}
`maleadal were prepared ata volinae cate ah iba These were mixed in.an agalie marar ip praduce a. mixture.
`fOUS3]
`inthe msulating outer cylneer, fhe sofid slectrotyvie material of he mwerive examole } which caorespanded ta
`a thickness of 00-yum, 6.34 mg of the above mixture, and 147 nag of Aj powder ware siacked inthe order, These were
`rressuremonied at a pressure af 300 MPa ta provide-a first elactrade and. asaid elactratyte layer,
`{0038} Next, a metal in ihickness: 200 pm} was stacked an ihe opposite side fo-fhe side which was mm contact with
`ihe first aleotrode of thesolic slectrobte layer. This was pressure-mokiad st a prassure of 88 MPa to orathice a stacking
`stuctire consisting of ihe first electrode, the solid electralyte layer, and a second electrode.
`0095} Nexi, stainiess-steel current collectors were disposed on the upper and lawer parts af.the siacking Sineitare,
`and current caliector leads were atlached to the currant collectors.
`
`Finally. an insulating fernie was used ta Ginck and seal ihe inside of the insuleting outer cylinder from the
`{G0968]
`outsiie aimoasphere:
`{6087} Thus, the secandary battery of the inventive evample i was produced.
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`hharqeDischarge Test}
`
`FING. 4 is a ataph showing initial discharge characteristics.
`fO098]
`{6089} The reguits showrin FiG..4 were: measured bythe following method,
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`

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`os &
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`ta
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`ag
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`aG
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`EP 3 736 837 At
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`400]
`2a
`
`in-other words, the secondary battery of the Inventive example 1 was disposed-in.e thermostatic chamber at
`
`0101} Constant current charging was pertammed at a currant vahie of 0.05 C rite (20 hour rete) with respect to a
`theoretical capacity of fhe battery, and the charging was terciisted at a valtage of 3.6 ¥.
`fIO2] The battens wes discharged aia current value af 09 C tate, and the discharge was termingiad at a vatlage
`oFP ay,
`fot Sa} As 6 resutbof the measirement, the intial discharge capacity of the secandary batiery af ihe Inventive example
`qT was 20 pAh.
`
`«<fnventive exarapies 2 ty 4d>>
`
`{WH be described.
`[6104] Hereinafter, synthesis and evaliation methods of Lina..V4s4MFleaEly
`
`[Production of Saiki Rlectronte Material]
`
`in the iwertive examples 2 to 44, ihe raw Mey powders were grepared in @ glove box raidiainadina
`{8705}
`andiow oxygen aimosphers having & dew point of -90 °C” ar jess and an axygen valiie af S pan or less
`{O406]
`in the inventive examples 2 to 21, the raw matedal powdersLICL YCly, and 2rCi, were prepared in.such away
`INaP LAA YC, 0 Ay = Gea}. (ifi-a} oe ate maolter ratio.
`fOO7}
`inthe inventive exanmyNes 22 fog. 25, ine raw maternal pawdlers LEDER Villa, and HAC, were prepared in-such &
`way thafligh Y€ls0 HCl = (3-36-a: Cite) oa at a moter ratio.
`fOSRy
`inthe inventive exanune. 29, the rawnraterial powders LIC] Libr, YCi,and nC, were prepared in-such a way
`thal LG) ibe: YCR.: ZrCly = Oc 9 0.5:0-8.5.et a molarratic.
`yy
`{O3H9]
`inthe inventive example 30, the raw material powdersLIC], Libr, YBr,, and 2rCl, were prepared in such. away
`ihal LIC? OLIBy 2 ¥Brac 2rCly =
`9 2.6705 704.at a malar ratia.
`{OT70]
`in theinventive example 31, the nav material powdlers LiCh, Li, YCand 2noly were preparedin such a way
`thal LHCED L@oYCig: 2rCl, = 1.52905 OS aba molar ratic.
`fit} in he iivenhve example 32, the raw matenal powders Lich, La Yi, ana Zell, were prepared in such a way
`aE LACH LHS Yin: Erflly = 404.5 : 0.8 0.3 Ste molar ratio.
`
`ftG2)
`in theinventive exatraph
`33, the rawnesterial pcwweders LIBT Li YBr3. €and 27C\, were: prepared in such a way
`thal LiBr OLA. YErg rly = 0-5 021 8.5.005 at @ molar rata,
`{G713]
`inthe inventive exarnple 34, the raw material powders LIC] LIBr, YBrq, and HICH, were prepared i. such a way
`
`that LAG): RiBr YBrg PACH, = 4: paceoS O.9 ata molar ratio.
`{Gt74}]
`in the Inventive example 35, the raw misterial powders LUM, LU Vig, and HEC, ware prepared in such a way
`that LIC) LL Vig: HEC = 75 7.8 Boothe ata molar ratio.
`fO915]
`inthe inventive example 36. ihe. raw material powders LBs Lil, YErg: aad HICH, were prepared in such.a way
`that LAr lif YBrg HICH = 0.5 0256.5 06.5 aba moter ratio.
`fOT1S}
`in ihe weentive examples 37 to a, the raw materiat powders LATYC, and 2rCl4 were preparedin such &
`waythaf ih: YOlg 2rChys = Chap Taha.
`fOtV7]
`in theinventive examoles 37 to 44, affer he nuiling orocessing using the planetary bak mill, heat reatnent was
`veriormead ato50-°C. for t hour in an Ar stmesphere.
`fOI18}] Except for these, the solid slectrotvie mfefiats of the inventive examples 2 fo 44}. were prepared in the same
`manner asin he above-desoribed inventive axamgle tL
`fe149}]
`in each of the iqventive examples2 fa 44, “vahie of 8 “value of a", and “element kimk of M" are shawn iq Table
`Fo which wil be deseribed later.
`
`fEvaluation of Lithtaumfon Concduchyit)}
`
`{6420}. Conductivily measurement cells of the inventive examples 2 fo 44 were produced in. the same manner as ©
`the above-described inventive exarapie J in. glove tox maintained in. doyiow oxygen atmosphere witha dew paint
`oF -G0. SC. or je