B kasupatsches
`
`motatot
`Eurouecti
`B
`B Potant Offies
`B Ofiey soraeden §
`: des heovety
`a
`
`
`li IATEERE
`I
`
`
`(1%)
`
`EP 3736 899 Af
`
`(12)
`
`EUROPEAN PATENT APPLICATION
`published in accordance with Art. 15344) EPC
`
`(43) Date of publication:
`T474.2020 Bulletin 2020/46
`
`{27} Agplicdtinn number 18868795.2
`
`(22) Date of fling: 13.11.2078
`:
`
`(84) Designated Contracting States:
`AL AT BE BG CH CY CZ DBE OK EE ES FIFR GS
`
`GRHR HU IE ISU LILT LU LY MC MK MTEL NO
`PLPT RO RS SESISK SM TR
`Resignated Extension States:
`BA ME
`
`Designated Vahdation Stetes:
`KH MA MDTN
`
`(30) Priority: O8OL2048 JP 2018000432
`
`{74} Applicant: Panasonic intellectual Property
`Management Co., Lid.
`Osaka-shi, Osaka 540-8207 (IP)
`
`(64)
`
`BATTERY
`
`
`
`{4} $RECL:
`ea a7eg Nee
`Homa topes82
`CONG 49/1g 20801
`COTF 17/0920aN
`HOM 16/052 eeeen
`HOTM ayep (2006.09)
`HOTM 10/0582 (P29R eR ype8
`
`,
`{5@} infemational application number:
`PCTASP201 8/04 1950
`
`{87} International publication number:
`WO 20797935323 {11.07:2019 Gazette 2019/28}
`
`(72) inventers:
`* SARAIDA Masashi
`
`Osaka-shi, Osaka 540-6207 {JP}
`* ASANO Tetsuya
`Osaka-shi, Osaka 540-9207 {JP}
`+ MIYAZAKI Akinobu
`
`Osaka-shi, Osaka 540-6287 {37}
`
`i74}) Representative: Griinecker Patent- und
`Rechisanwdite
`PartG mba
`
`Leopaldstrafie 4
`80802 Munchen (D6&}
`
`Provided is a betiery (1000) camprising a -catiinds (203), an strode (203) and ar dectoite layer id). Fhe
`i&?}
`glectroiyte bayer it} d}includes a first steciralyte fayar iid?) and a second alectrotte layer (102). Fhe firstostectralyte
`layer (Hiri p includes a firsh said alectroivie material (731). The second electrolyte tiyer (102) Includes a second. salid
`
`
`electraivie mataial which isa maledal different fram the first solid alectratyie matardal 414}. The first selid electralyie
`material (PP) includes inniuny, af je@ast-one Kira selected from ihe group cansisting of metaliioid elements and metal
`elements other then Hhigre, and atleast one hind selactad fromm the group cansisting of chlerine, bromine, and jocine.
`The first solid electroiie material (T37) dees not inchide sulfur.
`
`EP3736899Al
`
`
`
`HG. 1
`
`Prrted bydouve, S50} PARIS (FRE
`
`

`

`EP 3 735 869 At
`
`Description
`
`BACKGROUND:
`
`i. Technical Fisid
`
`fOO07] The present disclosare relates to-a battery.
`
`2. Description af the Relea Art
`
`{8002}
`
`Patent Lierature | discloses an alisold ballery using.a sulfide sok electrolite.
`Patent Lieratere-2 diccioses anali-sald batlery using.a haide inchiding tydhen a5 a solid atectriiyie
`
`TATION LIST
`
`Patent iierature
`
`{0083}
`
`ta
`
`23
`
`¢se Patent Apoication Publication We. 201-1 200%2
`Patent Liierature 1: Jag
`Patent bierature 2:
`Japanese Palent Agpication Publicaiion No. 2000-244734
`
`23
`
`SUMMARY
`
`in the prior art, suppression. of accumente of shart circull is desired.
`[0004]
`0005} The batiery according to Gne aspect af the present disciasure corniprises:
`
`a cathode:
`an anude; ang
`an sleciraiyte ieyer distosed between the cathode and the ance,
`wherein
`ihe clectrolyia layer iichides a frst nleciralyte iayerard a second elpctratyle layer;
`the first electrolyte layer inckudes & first satid electrofie materiak
`the secord elactralyie layer includes a second solid alectrohte material which isa material differant fram the fist
`sold electrolyte material:
`the frat-solid elactrable miatenal incides:
`
`aG
`
`ithiun:
`atleast one selected fromm [he group cansisting-of metalinkt ciermanis and metal elements other than ditties) aad
`at feast one kind selected fran ihe group condisting of chicting, bromine, andiodine; and
`
`the first solid ctectrohte material daesnat include sulfur.
`
`(6606) According. io ihe present disclosure, the accturence of the shart circull can Be sugpressed.
`
`BRIEF DESCRIPTION OF THE DRAWING
`
`BG
`
`{O0aT}
`
`FiG. 1 is a cross-sectional view showing a schamatic canfiguration of a Battery }O00Jn a first embodiment
`FiG. 2 is a crogs-sectionai view showing a schematic configuration of a attery }1)0un the iret. embodiment:
`FIG. Disa onoas-sectional view showing a schematic configuration of a heatiery 1200inthe first amibodiment.
`FiG_4is'a graph showing an Initial change characteristic ofthe batteriesin the inventive cuammle 7.and ihe comparative
`‘examiote.
`“I
`
`

`

`DETAILED DESCRIPTION OF THE EMBODIMENTS
`
`EP 3 735 869 At
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`os &
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`ta
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`ag
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`aG
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`{0008} Hereinater, an eribadinent of he presen disclosure wil bedeseripad with reference io ihe drawings.
`
`iFirst embodiment}
`
`FIG. 1 is a cross-sectional viewshowing a schematic configuration of a batlery 100d in ihe first embadiment,
`fO008]
`[OHO] The battery 1000 inthe first-ermbodiment comprises a cathode 207, an anode:202, and an electrolyte layer 18.
`[8014] The elaciroiyie isyer TOis: a layer provided bebweer ihe cathode 204 and the anode 202.
`M012] The electralte layer 108 inchudes.a fist electrolyte layer 101 anda second electratyie ayer Tao.
`{0013} The -fiest elsciralyia ayer 194 incluties a first solid slectralie maternal.
`fO074] The sacond electrolyte Jayer TO? includes a secaund solid alectralyte material, The second salid electrolyte
`material is a riaterial ddierani from the frst solid -dectoiie materdal.
`{6015} The irst solid electrolyte material is a material reureseniad by the following conipasiven formda (1+
`
`LiBip,
`
`Formula (44
`
`who, a, fp andy are valies larger than O.
`
`Mincudes at least one of meiaiioaid elements and metalefements other than Li,
`
`xis one or rore kinds of slements selected fram the group consisting of Ch Brand!
`
`{0076} According tathe above canfiguiation, oocurence ol shoricireult can be sunpressed in other words, is possitie
`to decrease isk of the shart circuit due to precipitation of a ithium metal al the fmeof overcharging. Pais can imorave
`safety. This.is srabably because, when.a lemaneor higher halide electraiyie is broaghtinto camtect with a him meta,
`ihe Nihium metal is cansumed by pertally reducing the temary or higher halide electrolyte, and further growth af he
`Nhu srietal is: suppressed.
`[OO17} The ier“yetaloki elements” are 8 Si Ge, As. Sb: ard Te:
`{G018} The term ‘metal element" refers to all clernents included in Groups fio T2 of the periodic fable except for
`hydrogen, and af ciscieaqis inched in Groups 73 to 1 of the perindic table except for all ihe mistalisid slaments, CON,
`P, G3, ard Se. nother words, the metal element becomes a cation, ifthe metal element forms an inorganic canmpound
`weth-a halide.
`
`inthe composiian jormana (1), M meq inckide Y= yitrura).
`{0079}
`in ather words, the firsi solid electraiyie matenal may inchate Y as a metetenrent:
`{G020}
`fo0u27] According to the above cankguration, jon conductivity of ihe first solid etectrolyie mater! can be further im
`proved. Thereby, the charge. / discharge efficiency af the hatlery can Ge further improved.
`{0022} The firstacld electrohte maternal inchuling Y may be_ jor exanigle, a compaurd reprasented Sythe composkian
`formula LigMegyMa{a + me +c =.0and em are satisfied) (Me: atjeast one of métaticid elements and metal elements
`other than Li and ¥i Gtr valance oumber of Me}.
`fOU23] As Me, any of Ma. Os, Sr, Ba. Zn, Se, Al a, Bi er, HE Th Sn, Ts Nob, ora mixture thereof may be used.
`{0024} Accarding io the aboveconfiguration, he ion conductivity of the fist solid electraivie matenal can be fucther
`Faproyed.
`{0025}
`inthe composiian jormuda (1), M may inchide Fe.
`{0025} Accarding tc the above configuration, fie fon conductvey af the first solid electrohte material can be furthec
`improved. Thereby, the charge / discharge efficiency uf the battery can be further improved.
`FORT} The first solid eiectroiyin matenalimay he Lig¥lg, LISVChg, Lig1g.gag qBrgvor LipFeCly.
`0028} According io the above configuration, ihe tin conduchvily af ihe fist solid electroivie nigterial can Ge Rather
`imoraved. Thereby, the change / discharge efficiency af the betlery ctay be hinherimproved.
`[0029]. The first solic electrolyte material may be a material represented byihefollowing cormposiionformula (Ag)
`
`Ligsaake
`
`Formule (AT)
`
`where, inthe composition formda iA}, X is bvo or more kinds of elements selected Tram the group consisting of CH, Br,
`and f.
`
`in addition, in the cormposifoen forada (A1}.0< d < 2 16 satisfied.
`{08030}
` Acourding io the above configuration, ihe ton conduchyity of ive fist solid clectrokhia nigteriaf can Ge Ruther
`POI9}
`imoraved.. Thereby, ihe change | discharge efficiency ofthe battery can be husther improved.
`[0032]. The first solid electrolyte material may be a material represented byihefollowing cormposiionformula (Ag)
`
`

`

`EP 3 736 899 Ai
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`Lig¥Xe
`
`Formuis (42)
`
`where, ithe campasition formula {42} * is two of mare kinds of elements selected from the groun consisting ef C1 -Be,
`anf
`
`$0033}. According to ihe above configuration, heton conductivity of ihefirst solid eleciroiie material can be tuche
`impraved. Thereby, the charge / dischargeefficiency ofthe battery can be further improved.
`{OUS4] The first solid electrahte matenat may he a raterial represented by the iollowing cormpusition formuta (AS):
`
`LisgsYq ygCly
`
`Formula (A3}
`
`where, in the compositionformute (AS), 9 < 32.0015 is satisfied.
`{G035] Accarding io the above configuration, the ion conductivity of the thst solid electraivyie matenal can be fucther
`Waproved.. Tharehy,he charge / dischargeefficiency of the hattery can be farther improved.
`{0036} The fret sulid electrolyie materia! may be a material represented by the following composition formula (Ad):
`
`Liggs¥y sBre
`
`Foarmuta (A4}
`
`where, in the compasitton formula (44),.0< 6s 0:25 is sadished.
`MOS7} According io the above conhquration, the tin conduchvily af ihe fist solid electroivie nigterial can Ge Rather
`imoroved. Fhereby; the charge / dischargeefficiency af the battery can be further improved.
`FOUSR] Thefirst solic ateciralvie material may be-a raterial represented by the tallowing carmposiion farnula (AS)
`
`LigauatqsahesCigoayBhdy
`
`Farmula {A5}
`
`where, ithe composition forma tA5), Me is one ar more finds of slements selected from the qraup consisting of Mg,
`Ca, Sr, Ba and Zn.
`{0039}
`in-eddiian, in the composiion farmmaa (AG),
`
`ego
`OS a 3;
` <{3-38+a}:
`<<(asa
`Fsxs8
`
`Bsys
`iM yy} < Beare sahished.
`
`os &
`
`ta
`
`ag
`
`fO40} According io the above configuration, ihe tin conduchvily af ihe fist solid electroivie nigterial can Ge Rather
`improved. Thereby; ihe charge / discharge efficiency afthe batlery citar be Tunher improved.
`FOUS 7] The first solict atectraiyte material may be-a rateral represented by he tallowing carmposition farnula (AGY
`
`aG
`
`LisgsgisphegCly.yny
`
`Fomula (A9}
`
`where, inthe composition farrnule iAS), Aleuis one cr mone kinds af elements selactad frora the aroup consisting of Al,
`Se, Ga and Bi.
`{0042}
`in-eddiian, in the commposHion farmmaa (AG),
`
`ix + y} 20. are satished,
`
`53
`
`0043] Accarding io the abave configuration, the jon conductivityof the first solid electralyie malariaboan be further
`qoiywoyed. Therety, ihe charge / discharge efficiency of the battery can befurther rmpreved.
`{GO44j] The first solid slactrolyte matenal may beasnisterial represented. by the iallowsr compasition fomniula (Asi
`
`

`

`os &
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`ta
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`EP 3 735 869 At
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`LegsatgahlegOlegybtyh,
`
`Formula (Ay)
`
`where, ih the composition formals (47), Me is. aneor roe kinds of elementsseiected fram the group consisting of Zy,
`HE and Ty.
`6045]
`in addition, withe cormpasiban formiugs VAs},
`
`
`
`P0846} Accurding to te above configuration. fhe tun canductivily of ihe dtirst solid electroiyie material can be futher
`improved. Thereby, the charge’ discharge efficiancy af the -batery can be further improved.
`eu47] The first. sahd alectraiyte material may be a maternal represented by ihefollowing caraposition formula (A&y
`
`LiggenagaagheyBigdy
`
`Formula (AS)
`
`where. in the composition formula (AS), Me is one ar more Kinds af elements selacied fromthe aroun censisting of Ta
`and Nb.
`
`{0048}.
`
`in addition, in the cornposifen fanmade (AG),
`
`
`
`futher
`
`70049} Accurding to te above configuration, fhe tun canductivily of ihe dirst sclid electroiie material can be
`improved. Thereby, the charge! discharge efficiency af the battery can befuriherimpraved.
`[OUSO] AS the first salid electralyte muferial, for exampie, Lis¥X,g, LioMaX,
`LigFeXy, LAR daa, Inika: oF Ligtll Ga,
`in ix, may beused.
`G51} The first elactraivle iayer 10} may include the test sald electratyie matenal as a main component. da ather
`words, ihe jist eiectraiyie layer 1a} may includethe first salid eleciraiyie maheanat, for examme, sf awenght ratio of nat
`fess than 59°: (netiess than Soc ty weight to ihe entre first clectratyie layer 101,
`fOUS2] Accordingio the above canfiquration, the charge discharge characteristic of the battercan be further improved.
`Furthermore, the abcurrence af the shert cireuil can be further suppressed.
`{0053} The first electraivie layer 10) mayinclude the fist sald electroiyie maternal, for exanipia. ata weight nalig of
`notiess than’ 70% {not hess than 78s by weight) in the entire first electroiyfe layer TL.
`(0054) Accardingin the sbove configuration, he charge / discharge characteristic. ofihe batiary can be further improved.
`Furthermiare, ihe occurrence of the short cimint can be further suppressed.
`[OG55} The first dlectrolyte layer 167 nay firdher include Incwtable impiuddies. The fwst elactralyie layer may inchide
`ihe starting materials usedfor the synthesis of the first solid electralyie oatenal. The first electrolyte layer may include
`ineproductsor desampostion prodects. generated when the firsi solid elactredyie matefalis ayothesizes.
`Ouse}
`in additian, ihe first electralyte Jayer-1O) mayichicie the first valid elactraivie material, for example, ata weight
`ratof TO0S CIOs by weighi} io the antirefirst electratyie layer 101, exceptfor ihe inevitable impurities.
`
`{OS7] Acvordingia the above configuration, the charge! dischargecharacteristic uf the battery can be further naproved.
`Farthermore, the occurrance of the short cireuit cart be further suppressed.
`{8068} The first ciaciraiyie iayer 104 may be compased-oanhy of the firsi saihd clectralyie mataral.
`fOUSS} As the secound solid clecinayie maternal for example, a sulfide solid lectralyie, an oxide solid clectroiyfe, or
`an organic palyraer salid electrotyie maybe used.
`{0080} As the sulfide solid electrolyte, LigS-PoSg, LSSiby, LipSHS 4LipGeSy, Lig onlSyonPy patty, LpGOP25.15
`may be used.
`jOUS4}.
`in olherwerds, fhe second solid clectrolie material may be a sulfide sold stlectralyte. in hie case, tie sulfide
`
`

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`EP 3 736 899 Ai
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`sald electralyte may include ithium sulfide and phosphorus sulfide. Far exarnple, the sulfide acid clectroiyte may be
`LigS-PaSs.
`{8062} According id ihe above configuration, the ton conductivity balween the cathode 201 and the anode 202 can be
`further imoroved.
`{0063] As the oxide solid electraiyie, a NASHOON solid electraiyie such as LYngPO.).sand its alement substiution
`products, a{LalnhiO., peroyskite sole aeciralyte, a LISKION sole electrolyte such ag Li,FniGesO ye, LighiOy, LbBeOy
`andits element substduticn producis, a gamet solid electralyte suchas Li;Las71O jy and fis clementsubstitution products,
`LigN and its H substitution products, and LisPG, and ts NM substitulion products may be used.
`0064] As the organin solymer solkd electrolyte, for example, a cormpauad of a polymer campound and 3 thin salt
`can be -used The polymer compound may have anetiyviene oxide structure. Crueto the athyvlens oxide stuctire, 4 large
`amount of lithhim sail can be inched te further Increase the ing canductivily. As the Hthhuay sak, LPP.LBP. LSB,.
`LIAS, LISOAOF2, LINISOLCF .},, LIN(SO5CoFoo, LINISOLCFsNSGICFgh, ofLIC(SO5CFsj, maybe usad. As theithium
`sai cone dithiant sat selected trom these say beused aipne, Atiermatively, a dixture of bya or mare kinds of tie idhium
`salis selected from these may be used asthe ithaim sait.
`fO085] The secon) electroiyie layer 102 may ichide the second solid alectrolyie mafenat.as a main cammponent. jn
`other wards, the secand slenbotte layer 102 may include the secandsalid clectrolyie maternal, for exarniple, abweight
`ratio of notfiess than 50%that tess than S88 by weildht} fo the entire second electrofyte layer 102:
`[8866] Accordingic the above configuration,the charges discharge characteristic of the battery canbefurther improved.
`fOOR7} The second electrolyte iayer 2 may inchice the second sold clectroiyie material, for example, atweighti ratio
`of motiess than 708s inailess than 70% by weight) id the entire second clectroivis layer 72.
`{8068} Accordingio the shove configuration.ha chames discharad characteristic of the battery pan-be further improved.
`fOU6S] The second electrolyte iayer 102 may furher include inevitable irmpunties. The second efectroivie layer may
`inciude the sterling matedals used forthe synthesis af the senonud said electrolyte maternal. The secand slecirolyte isyer
`fay include by-oroducis or decompositen products generated when the secand sold slectrolyic material is synthesized.
`{GOTO}
`in -adeiion, ihe seconelectraivie layer TO2 may inchide the second salid elactratyle maternal, for exarniple, ai
`a weight ratio of THs (160% by weidht fo the aniire second slectrafyia layer 102 excemt far iheinevitahte inmuriies:
`{8874} Accordingic the above configuration,the charges discharge characteristic of the battery canbefurther improved.
`{[O872} The secand alectrohte yer do? may be campased only af the secand-said alectmoivie material
`{O73} The firstelectratyie layer 10) andthe second siectraiyie layer 102 mayinclude Iwoor more Kinds ofthe materiats:
`described as ihe scdid electioivie material. The sane. matecal may be included in te-tiestelectraivte iayer 101 and ihe
`
`second atectroivie tayer 12. Cifferant mmateriate nmay fo used. depending on a property of each bayer.
`
` Thethicknessof the electrolyte yer HG may be nal less than. 7 ym.and net spore than HH) pin. ifite thickness
`{G074}
`ofthe slectrofyts layer. 100 is jess Than 1 wim, the possibility of the shor circuit between the cathade 204 andthe anode
`202 is Increased. In. addition, i ihe thickness of the electrolyte layer 100 is more than 100 gm, the operating af high
`aufputimay be difficult
`[0075] The calhiode 201 inchides 8 material having a property af staring and mleasing metalions Gor exampie, Hihum
`jons}. The cathode 201 includes, for axarmple. a cathode active riateriai (lor example, cathode active material particles
`2Etb
`{0076}. Examplesof the cathode aciive material inchide ithium-sontaining transilien metal axides
`Or LiCoOs}, ransiion metal fluorides, polyanions, huornated polyanion materiais, fransitien meotai‘sulkes, arnsition
`metalexyRuoridas, tarsition metal exysulfides, ane fransitinn metal oxynindes.
`fQorTyF] The cathade active material nay beun caballate. For axanypie, the cathode active material may be LiCaG,.
`Thereby, the charge / discharge efficiency of the batfery can be further improved.
`{O078}) The thickness of the cathade 207 may be not fess than 1 pm and motmore then S00 pen. ithe thicknessaf
`the cathode is jess han 10 pm, if may be difficull io Secure an.energy densifyof the battery sufficiently: if the hickness
`af the cathode is mate ian 500 pr. the operation al nigh oulpatmiaybe diffe:
`{G079} The anode 202 includes a maternal having Ss propefy of storing and releasing metal ions (e.g. tithium fone).
`The anode 70? inchides, forexamule, an-anode active mater
`fouSny
`Por the anode active material, a metal rmaterial, a carbon material, an oxide, & rife, atin compound) ora
`siican compound may be used. The metal materiat may Gea single metal Allemativel:, ihe metal matenal may tear
`alley. Examptes af the metal material inciinte.a ithiura metal anda lithium alloy, Examples afthe carbon niaterial intude
`
`(e.g. LENE CANO,
`
`natural graoivte: coke, graphitized carbon, carbon fibers, spterinal carbon, arifices! qraghite, and amorshuus carbon.
`rors the viewpaint of capacity dencity, silicon (8!)tin3 {Srf)4 sHicon sampound, ora.lin compound can te sutably used.
`jOUS7} The thickness of the anade 202 may be notless than VO gm and not more than S00 pnHfthe theckness of the
`anode isdess than TO pm, itumay be dificull jo secure an energy density afihe battery sufficiently.
`in addition, # the
`imickness of the anode is pore than S00 am, the operation at high uur may be chMcull.
`fO082}] The cathode 20) may inctude the above-mentioned sufidie solid alecteohte, Ine aboverneniionad oxide
`
`ealacinaiyte, or te above-mentioned organic polymer solid electrolyte far ihe purpose of enhancitg the ian conducthsty.
`
`sai
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`

`EP 3 736 899 Ai
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`fGOR3} Alleast one ofthe cathode 701 andthe slectroivie kwer TOO may inclide a non-aquecus électrolyte safutan,
`& ge! eleciratyie, or an ionic. Nquid for the purpose of fackiiating exchange af fithkim ions and Improving the oulpul
`charecharistic of the baller.
`fOU84]. The cor-aqueous elective solution inchides a non-aquecus solvent and a lithium salt which has beendis-
`solved in the han-aqueonus sohvent As ths nonagueces salvent.3 cyclic carbonate solvent, a chain carbonate saiverni,
`a@ cycle ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester sofvent ora Horne solvent may be
`used. Examples ofthe cyclic carbonate spivent nciode ethene carbonate, propylene carbonate, and bulylone carbonate:
`Examples of the chain carbonate selvent incite dimethy! carbonate, elhyt methyi carbonate, and diethyl carbonate.
`Examples of the oyclic einer solvent Inciode tetrahydrofuran, 1.4-cdicmane, and } odioxalane. Examoies of the chain
`siher solvent include 1 2-dimethaxyethsne and 1 2aliethoxyethane. Examples of ihe. oyelic. ester solvent include y-
`bulyralscione. Examyptes of the chain ester sobvent include methacetate. Examples af the duorine solvent include
`fuoraeathyiens carbonate. methyl fuorocropionate, fucrobenzene, fucretyd metcarbonate, and Tuorocdimethyviens
`carhoriate. As the non-aqueous solvent, cne non-aqueous sobvent selected from these may be psed alone. Akernatwvely,
`st combination of two or mare Kinds nf the nan-aqucoussaivenis seincted fram these may be used.as the Ran-aqasaus
`
`saivent, The non-aqueuisciectratyie solution niayinclude atleast one fluorine solvent selected! framthe graup consisting
`of fueroethyiones carbonate, riaihyd Rueroprapienate, huarcbenzene, Suoroetind maihy! carbonate, and fluoredimethyt
`ene tarbonate. As the Whturi salt, LPF, LIBF, LISBF,, LIAsF,.. LiISOsCK,,.. LIN(SO5EPs)5, LIN(SOjCara}y,
`LIN(SOSCF,SO.0,F9). of LIC(SO,CF4}, may be used. As the fittium sail, one lithhud? sail selected framthese may be
`
`used siong. Aerniatively, a mixture of hwo or more kinds of hin salis selected from ihese may be used as the fihium
`sail The concentration of the hifium sali, for example, white a range-cf OS to 2 omials fer.
`fG085}) As the gelelectrotvie. a sober risterial including Ihe non-aqueous alectrohte salition may ve used: As the
`polymer maternal, polyethviene oxide, pmyacryioniiriie, pokrvinylidene firorcde, pofymeihy! methacriate, or o pahyner
`having an effiviere cide bond ray be used.
`PCRS] The catien forming the joie hqua may be:
`
`an aliphatic chain quatermary salt such as tetraatkylarnmoniumor tetraalkyiphosphonitun,
`aliphatic cyclic ammonium such as gyroidinium. marsholinkan imidazalinkum, tetrahydrapyrimidinkan, pigerazia-
`iQ. OF Sipe, or
`a nifragen-coniaining heterocyclic ansmatic cation such as pyridinivuen ur imidazoinni.
`
`ioge7} An anion forming the Jomo liquid is PFe. BFy, SaFe. ASFe, SO.CF,, NISQ.OFsiy. NGO.F sin)
`NISCHEFSNSOoCFgh) or CHSOSCE gig”. The tonic liquid may include a ihbkun salt.
`POOkS8] At least ane of fhe cathode 201, the electrolyte layer TOO, and tre-anode 202 may include a binder forthe
`purpase cf improving the adhesion behween the particies. The binder is usec io nmprove the binding property af the
`materia: forming thé electrade. CXamples of the binder include pofwingidens fionicde, colvielratiuoroethylene, peabyeth-
`\iene, polypropylene, aramid resin, polyamide, palyimkia, polyamilesnide, palyacnsanirite, palyacnic acid -meathy!
`polyacrylate esterethyl polyacrylateester, haxyt polacrpate ester, solymethacrylc ackl, methyl pohenetiniondate ester,
`sihy! palymetihacrylate ester, hexyl polymetnacrpiste esier, polyvinyl acetate, polywinyipyrrolidene, polyether, polyether
`sutfene, hexefitioranalyptopyiens, styrene butadiene nibber, anid carbaaymethyicaiuings..As the bender, 8 copohnrer
`of iweoor more kinds of materials selected from tetrafiuorcethyiane, hexafiuoroeihyiene, hexaflucranropylene, periuar-
`galkyl vinylether, vinylidene force, chioratrifivcresthviens, athens, croydene, pentiafluarprapylene, fluaromathyi
`vinyl ether, acrylic acid, and hexadiene may be used. iv addition, hve ur more kinds of selected from ese may be mixed
`and used as the binder.
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`in addition,.at leastane of the eathade 207 and the anade 207 may inchide @ conducive agent as. necessary.
`{0089}
`FOOSOy The conductive adent ss used fo reduce cietirds resistance: Exanipies ofthe conductive agent inchide aranhite
`such as. naducal Graphite or artificial graphite. carbon. biack such as acebtdene black or ketjen black; a conduchve liber
`such as 3 carbon fher.or a metal ther: carbon fluoride: metal powder such 46 sluminuny conductive whiskers: such as
`Finc oxide-or polassinimtense: & conducive meialb oxide such a5 Wentum oxkie, and a conductive polymer compound
`suchas palyanting, polypyirohe, or poalythiophens. Cast reduction can be achievedby using carbon conductive agent
`as the canductive-egent.
`P0084} As shownin Fic. 1, the tist electrolyte layer TO) may be provided between the cathode 20) and the second
`electrolyte layer 102.
`{8092} According tc ihe above canfiguration, the fon conductivity between the cathode 201 and the anode 202can be
`furier imoroved. Furtiermore, the occurrence of the shart circuit can be further suppressed.
`{6083} Asshownin FIG 1, the first eleciralvie layer 1041 may be posdianed withoul being in santactwith the anade 202.
`f0S4a}>Acocurding te ihe above configuration, the fon conduotivily between the cathode 207 andthe anode 202canbe
`further imoraved. Furthermore, the aonarence af te shart cicuiican befiner suppressed.
`[0095]. The cathade 2074 may inmelude the first solid clectrofyte material.
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`{0098} According io the above configuration the-jon conductivity between the cathode 201 andthe anade BO? carn be
`further imgravedt.
`{0097}
`FIG. 21s 4 cross-sections! viewShowing a schematic configuration. of a battery J1Qddn ihe first erbadiment.
`[S098]
`inthe battery 1100 accordingtu thefirsl embodiment the cathode 207 includes a maternal mixtureof first salid
`electroivie garicies P41 and cathode active material pardicies 211.
`§O089}. Each uf thefiral solid elecinsivie panicles TTT may bes particle composed of thefirst salt electrohte maternal
`or a .paticke incivding the frst said eleciraivie matanalas @ raeht component at 3 weight ratte after examele, natiess
`than 5096 inot less than. 50%by weigh!) fo the enlire of the first solid electralyie particle 144 .
`(100)
`in-additian, a shepe of each of the frsisoalld electriiyie particles. 117 in the first amborimentis nat particulary
`tmited ard may be for example, an-acioular shape, a sohérival shape, or an eiintical sphencal shape. For example,
`ihe shape af each of the first sold electrolyte parlicies 131 maybe. padide.
`fOto1]
`For example. ifthe shape of ie first solid elactrofie panticie. 11) i the first embodiment is particulate fe.c.,
`spherical). the madian diameter thereof may Ge net more than 200 ani. W the median dismeter is more than 100 pm,
`there is. a possibility thata goad dispersiin siete. of thecathode active material particles 27-1 and the ficst sailsetectralyie
`particles })1 fats fo be formed in the cathode matenal. Therefore, the charde / discharge characteristic s lowered. jn
`ihe first embodiment, the median diameter may be nol more than id pm.
`[6182] According to ihe above configuration, a good dispersion stale of ne cathode active material partictes 211 and
`thie tirst salid electrohe gariicies J14 cart be famed in the sathade 20T,
`{O03}
`n-adeltinn, in ihe: first erncbodiment, the first solid electralyte particisles. id may be smatier than the median
`thameter of the cathode active material particles 271.
`F004} According io ihe above configgrating, a batier diapering stein. af the fest solkt clectradvie padicles 117 and the
`cathode active material particles 214 car he formed in the electrade.
`{G705}0The median diameter of the cathode aciive matenal particles 271 may be nel legs than 8.1 pny and ned more
`than 700 pam.
`{O105})
`ithe median diameter of ihe cathode active malenal particles 214 is jess tran 0.1 am, thereisa possibility
`that-a qoad dispersion state af the cathode active material particles 211 and ihe first solid shectrolvteparticles 1177 fatis
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`ta be formed in the cathode. As ayesutt, the charge ¢ sees cheracteriate af the battery is lowered. in. additios, if the
` fed
`Median diameter of the cathode aciive matedal particles
`271 Is morethan 100 pm, inhidiffusing in He cathode active
`material particles 234 is made slow. As a resul, the aperation at high output of the batfery may be diffiguit.
`f4tO7}) Fhe median diimeder af the csthoade active material varticies 214 may be larger than the median diameter af
`the first solid electrosvie particles 444. Thereby, a goud dispersion state of the cathiie active maternal particles 214 and
`the first sdliid dlectroivie garlicies 114 can be fared.
`fOd08}
`In addition, he cathade 24 may include @ pluralaf the frat solid electrofyts particies 14and a plurality af
`the cathode active maternal panicles 271.
`[O108} The content of the first solid clectraftte particies IT1 andthe carter of the sathote active material particies
`2:9 inthe -oathade 20may be the sameas or differant from each ather
`fO910} WHA regard feoa volume catia “v ¢TOvi-v" of the cathode active material and the fist solid electrolvie material
`included in the cattiide 201 SR <v 2.05 maybe satisted. ify s30,dimay be diticuk to-secure arenergy density of the
`Batiery sufficiently. iaddition jf v> G5. the operation at high Gutopt may be ciffican.
`fOV1] FS. 3 is 3 cross-sectional view showing & achemate comiguration of a baflery 1200 in thefirst embodinient.
`[6712]
`in ihe batiery 1200 In the first ambodiment, ine electrolyis layer 100 inchudes a third olactraiyfa fsyer 103.
`fOI13] The third electroivte layer 103 is pravaied behween the cathode 204 and ihe first elactraivie layer 101.
`fits} The cathode 20) anc the thied electrolyte layer 102 Include a suite solid electrahyte.
`{0145} Accarding fa ihe above configuration, the ion conductiviy between the cathode 207 and the anode 202 van be
`further improved.
`[0316} An example af ihe shace ofite tettery in the firstambodimant is. 3. cain. s cylinder, avansm, asheet. a bullen,
`a Raf type, ora stacking structure.
`
`“Manufacturing Method of Firsf Soatid Electrotyie Maternal
`
`{Hi7] The first solid slectrolyvte material inthe frstembacimentcan be produced, forexample, by fhe folowing methad.
`{0178} Binary halide mw material pawtlers. are pragared sn-as ta provide a tdendingrate of 4 target compadsition. For
`example, if Lig’Cig is produced. LIC] and YCl, ere preparad ata melarraie of 3:7.
`JO179] At this Ume, "MM", “he", and "XM" in the-above-described composition formula can fe determined by setecting
`the Kinds oftheraw material powders. dn acddiien, the shovementonad yalues “w") "B") “y")“d")"E") "at, "x" and “y" can
`be adiusted by adjusting the raw matenals, the blending rata and the synthesis process:
`{@t20] The raw matensl powders are mixed well, anid ihen, tbe raw material powders ans mixed and ground ta reset
`by 3 machanochemical miting method. Altematively, the raw maternal powders may be mixed well, and then siniered in
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`{@t21} Thereby. 2 sold slentrolyte material including a crystal phase as descnhed abeve is provided.
`{0122} The sanfiguratian af ihe crystal. phase the crystal structure}in the solid alectrolyte material can be determined
`hy ackusting the reaction methad-and reaction condifions of fhe raw maternal powders
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`EXAMPLES
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`[Ot23] Heremnater, detais of he present disclesure wil he described
`ihe comparaiive example.
`
`with reference tu the iyventive examples and
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`Gnvenive examine
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`[Production of First solid elaciralyte material]
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`bra dry woe wiltia dewpaint of -30 °° of bees, raw-patenal powders Liland Yi, were prepared ata
`P28]
`mojer ratioof La oY, = 301. Thesewere ground and nwinein amortar. Subsequenily, milling processing was performed
`
`at Boo rr for 45 hours using a planetary bal mt
`{0725} Thereby, a gowder of thefirst solid electrolyte, material LipVig which was a halkle solid alecirolyte inchuding.a
`crystal phase was provided.
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`rPPresfuction af Second Satd Electrolyte Material
`
` inancuargon glove bco-having arr Arstmasphere with a dewpoind o