a li Seemeeeas poemRoonaan
`
`l
`
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`
`B kasupatsches
`motatot
`B
`Eurouecti
`B Potant Offies
`B Ofiey soraeden §
`: des heovety
`
`(1%)
`
`m “0 bn ovalpe Oo HA sant oo ‘pb woods
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`}
`
`EUROPEAN PATENT APPLICATION
`published in accordance with Art. 15344) EPC
`
`(43) Date of publication:
`92.12.2020 Bulletin 2020/49
`
`{27} Agplicdtinn number 189802703.5
`
`(22) Date of iing: 12.12.2048
`:
`.
`
`(84) Designated Contracting States:
`AL AT BE BG CH CY C2 DE ORK EE ES FIFR GB
`
`GRHR HUTTE IS IT LILT LU LV MC MK MT NL NG
`PLPTRO RS SE-SISK SM TR
`Designated Extension States:
`BA ME
`Resignatad Vatdation States:
`KH MA MO TN
`
`(30) Priority: 26.04.2018 JP 2078077528
`
`(77) Applicant: Panasonic Intelfectual Property
`Management Ca., Lid.
`Osaka-shi, Osaka $40-6207 {JP}
`
`(72) inventors:
`> SUGIMOTO, Yuta
`Osaka-shi
`
`Osaka 540-6207 (IP)
`
`{54}
`
`BATTERY
`
`
`
`{4} $RECL:
`HOIM foss2OF
`COTG 25/04 200802)
`Hogay 47g 2006.09)
`
`pore 1799Men
`HOIB 1/06 1.08)
`HOFM 10,053109)
`
`{86} international application sumber:
`PCTIIP205 Bi045586
`
`{87} Intemational pudlination number
`WO 20197446294 {01.09.2019 Gazette 2079/34}
`
`* SAKAL Akihire
`Gsaka-shi
`
`Osaka 840-8287 {IF}
`* SASAKLfzure
`Osaka-shi
`Cisaka 540-6207 {IP}
`* MPYAZAKL Akinobi
`Osaka-shi
`
`Osaka 540-9207 WIP}
`
`(74) Representative: Griinecker Patent- und
`Rechisanwaite
`PartG mba
`Lenpoldstrafiie 4
`80802 Munchen (D5}
`
`Provided is 4 battery having further improved charaingdischarging effiinency. The battery coraprises a pasitive
`iBf}
`elecirate, a negative electrode. and an. alecirohte teyer providsd. batween the pasitive elecinade and ihe negative
`electrode. The electrolyte layer includes a frst electroiyte layer and.asecond electroiyte layer. The second electrolyte
`layeris provided beiweenthe first electrnivie layer and the negative elsctrade. The first electrohyte Iayer includes a firsi
`atid elactrafvie. material. The second electrolyte hayer includes 4 second solid electrotle roaterial that is a material
`different tramthefest solidelectrolyte miaiedal, The firsi gold electrolyte material inchides Li Mand % anddoes not
`inchide sulfur. M4 includes af ast one selected ram the group consisting of metaiiant eiements and metal slements
`other than LicXis atleast one selected front the group consisting afC), Br. and L Thereduction potential with regard tu
`fiiunraf the secand anid electtalyie materiatis jowerfhan the reduction potential with regard te lithium of the first solid
`electratyhe materist
`
`EP3745518Al
`
`Printed bydauve, 75007 PARIS (FR)
`
`(Cont. next page}
`
`

`

`EP 3745 518 Al
`
`201
`
`101
`
`202
`
`102
`
`100
`
`FIG. 1
`
`

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`ta
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`EP 3 745 518At
`
`Description
`
`BACKGROUND:
`
`i. Technical Fisid
`
`fOO07] The present disclosare relates to-a battery.
`
`2. Description af the Relea Art
`
`{G002} Paiant Lisrature.] discloses an albacid battery usind a halide inchiding Indhum a¢.a solid electrolyte
`
`CHATION LIST
`
`Patent Literature
`
`2
`SPASPIAfaSito
`Z
`fOUO3} Patent LHerature 1: dapanese Patent Application Publication No.
`
`
`
`SUUMARY
`
`in the prier art further improvement in charde / dischame eficioney of 4 battery is desired.
`{8004}
`fO005] The battery according to one aspect of the present disclosure comornses:
`
`8 positive electrade:
`anegeive clecirade: and
`an eletiroivie layer oroviced betweenthe positive atectrode and the nedalive alecirade,
`wherein
`
`the lectohyte Jayer eludes a first eipctniyia layer anda secand electoohte. layer,
`the sdoond eleciroiyie layer is provided between ihe Ntat siectrolyie layer and the negative electrode;
`the first elecirahte layer includes a first sedid cinciralyia maladal:
`the second alectroivie fayer inchides a second solid etectraite maternal differant from ihe first solid ohectraiyte
`materia:
`the first solid clectroiyte nigteral inciudes Li, M, anc X, and does not include sulfur:
`Mos aileast one selected from the graup consisting of metaliaid clemendis and metal elements other than Lt,
`Mis at feast one selected from the groun consisting of Cy, Brand band
`8 tecuctian potential wih regaetl to histund of he secondsalid alectrohte metenal is lower thean:.a rechuction potential
`with regard to lithium of the first solid electrolyte material
`
`{G008} According tc the-oresent discinsure, he charge / discharge elficiency of he battery can be miproved:
`
`BRUEF DESCRIPTION OF THE DRAWINGS
`
`foou7}
`
`FIG. 1 shows @ oress-sectional view of a battery 1000 in.a first enrbodiment.
`FIG..2 shows @ Gfass-sectional view ofa batlery 7100 in the fwst ermbediment,
`FRa. 3 ise graph showing aninitial charge / discharge characteristic of ihe batfenes- in the inventiveexample } aga
`ihe comparative examgie 4
`
`DETAILED DESCRIPTION OF THE EMBODIMENTS
`
`{GO08] Heremafier, embodiments of the
`
`present disclosure wil be described with reference to the drawings.
`
`(First embodiment)
`
`fOOHS} FR. fs 8 cooss-secttional view showing 4 schemafic canfiguration of a battery 1000 in the first embaciment.
`{8070] The tattery 1200 in the first embodiment sampises a postive electrode 204, a negative slectrade. 203, and
`an dlectralyie tayer TERT.
`
`

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`os &
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`EP 3745 518 Al
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`{G07} The slectralve layer 100 is provided between the pasitiveelectrode 204 and the negalive electrade 207.
`{@042} The electrotte layer 108 inchides a first elertrotyte layer 101 and a second clpciroliyie tayer 102.
`{8043} The second elecimiyte layer 112 is provided betweenihe frst electrolyte lever 101 and the negutive electrade
`
`RO1d] The first slectrohte layerdod inchides is frst salid electralyie mateacdal
`§015}. The second slectalyie layer 152 includes a second aetid electroiyie mmatenal, The second sotxt elsctrofyie
`material is a oraienal diferent irom the first solid electralyte maternal.
`O08] The first said electrahte material is a maternal represented by the following composition formate C3).
`
`Lightgk.
`
`Formuta it)
`
`wher
`
`3 and ysre each independently a value greater than 0.
`noludes atleast one selected fram the group cansisting of metaiinnd elements and metal elements other than Li.
`AS5 at least one selected fromm the group consisting of Ci, Br and |.
`
`[8617] The reduction gotentsl with regard folithium ofthe second scald electrohie material is jowerthan the reduction
`potential with reqard-to itivun of the first solid ehectraipie material.
`{048} By using the second solid alectroahte material having a how reduchon potential, reduction of the first sald
`electrolyte material jonmed of the Halide solid elacirdivie having high pore conductivity is suppressed. Thereby, the
`charging / discharging efficiency of ibe bathery can be improved.
`{6079} Theterm “meisilcit alemen? usad in ihe present specificationis at least ane selected frarn the group consisting
`ob Si, Ge As, Sh and Te.
`{8020} Theterm "mein elements” used in ihe present specification inckhides
`
`0} af eferients tnchided in Groug. 7 ie Greup Ja af tie Periadic Table lexcept for hydragen},. and
`GF all-ciarments ingheded bi Group 13to Graug 36 af the Penocic Table texcept for 5, Si, Ge, As Sh. Te, C, N,
`3S, and Se}.
`
`inother wards, wach of the metal elements beconies 3 cation, each af tha metal elements farms an inarganic
`fO0U27]
`campound with a badegen- compound
`(8022)
`inthe composition formula (2), A may inchude ¥ (mamely, vittiurn). In other words, the fst solid electrolyte
`maladal may Include Y a5 the meiatelement M.
`fou23] Accardingto the above. configuration, the ianic comiuctivity of ihefirst solic electrolyte matertal can be further
`raproved. Thereby, the charge / discharge efficiency of the baffery cart be further improved
`{0024} The first solid electrolyte matenal including Y may be, for example, a campaundrepresented by 4 composhian
`formula LiMenYX, (a+ mb + 3c = 6 and c >0 are satisfied} (Me: at feactone of metatiok! elements and metal elements
`other than Li and ¥i Grr valence of Me).
`fOU25] Ache, af least one selected from the graup consisting of Ma, Ca, Sr Ba, 7m Se, Al Ga, BierHi, Th Sn, Ta,
`and Nb may be-usad.
`P0026] Accurding fo the above configuration, the-swmice canductivily of the first sulid elactralyie material can be further
`Haproyed.
`{G027] The first solid clectrolyte material may be LipsVqgdig alle.
`fOO2R} According to the above. comigunstion, the jonic conductivityof thefirst salicleciralyte material can tre further
`Iniproved.
`{029} The first sulid clectrolyie mafarial may be a maternal represented by thetowing composition formula(Aq).
`
`Licad¥hs
`
`Formula (Aq)
`
`where, in-the.composition formuge (Ad) X ts hwo or more kinds of elements selected fram the group comeisinig of-Ct, Br,
`ened}.
`
`in the cormpasiion formiuda (Ad), O< d< 2 ioantished,
`{8030}
`fous According ta the above configuration, the ionic conductvity of the first solic electrolyte matertat.can be further
`aproved. Thereby, the charge / discharge efficiencyof the batten: can be hirther huproved
`0032} The first sake electolyie material may be & maternal represented by the folowing compositionfonnuisa(AP)
`
`LinyXs
`
`Formula {A2)
`
`

`

`EP 3745 518 Al
`
`
`where, Inthe composition faranda (Ag), < is hwo or more hinds of elements seiected Tram the group consisting of C1, Br,
`and. in other wards, ia ihe composition fomiula (At), d = } may be. satisted.
`fOU3230According to the above cormiquration, the ionic conductivity of the first solid electrole material can be further
`waproved. Therety, the charge / discharge efficiency of the battery can be further improved
`§03d} The frst solid clectroiyie material may be a material represented by the following composition formusa(A3}.
`
`os &
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`ta
`
`ag
`
`aG
`
`Liss s¥ qagtels
`
`Formua (AS)
`
`where, in the composition farmula (43},.0 < 28. 0.15 iosatsted.
`{8035} According to the abowe configuration, theianic conductivity of the first solid electroivie matenal car be further
`impraved. Thereby, the charge / discharge efficiency of the battery can Re further improved,
`{G036] The dirst acid clectroivte material may be a material represented by the following composition formala (Ad).
`
`Lig.gaVgush
`
`Formiute (A4}
`
`where, im ihe composition formula (A4}. 0 < 3< 0.25 is satisfied.
`[0037] According.io the above configuration, hedonic conductivily of ihe Hirst satid electrolyte material. can be further
`miproved. Therety, the charge / discharge efiencyof fhe battery can beturther inmpraved.
`{028} The first solid clectrotyie maisrial may be a maternal represented by thetowing composition formula(A5).
`
`Liggaat aableallg.,Ardy
`
`Forfaile (AS)
`
`3
`¢
`where. in tke composition fornia (45), Me i. al least one selected from the graug consisting of Mg. Ca, Sr Ba, and én.
`{0038}
`in addition, in ihe composiion formula {45},
`
`XR
`<a By
`Gs (A3atay
`OCT Hiak
`G2 K 28;
`Gey s &and
`ix + y}=-8 are salistied:.
`
`foudo] Accarding'to the above. configuration, the ianic comiuctivity of thefirst salid electrolyte material can be further
`raproved. Thereny, the charge / discharge efficiency of the baffery cart be further improved
`[OG44} The first solid Glectroiyie materiel: may bea malenal represented oy the Polliewing camposiion formals (As).
`
`Lisgs gigMegeyBry
`
`Formuls (AG)
`
`where, in the composition forme (AG), Meis atleast ane selected fram the group cansisting of Al, Sc, Ga, and Bi
`P0082}
`inthe camposition Jorma (A6},
`
`“pose i
`Ba = 2;
`O< (i+th-ay
`fy 2.8;
`Bays and
`ix+ y¥IS6 are Satished,
`
`[0043] According to the above configuration, the ionic conductivity of the first solid electrolyte material can be further
`impravad. Thereby, the chame / discharge efficiency of the battery can be hadher improved.
`[0044]
`Thefirst Solid sleotrolyte. materini may bea material represented bythefollowing compasifion formida (AT).
`
`Lig.gseVaegialleglsyyBrdy
`
`ore (A)
`
`where, in ihe composition fonnula (AT), Me is alleastone seiected fram. ihe group consisting of Zr, HY and Ti.
`fOudS}
`inadcifion, in ihe comoosifion fomula (47),
`
`

`

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`EP 3745 518 Al
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`
`
`M046] According io the stove canfiquration, theionic conductivity of the first salid electrolte material can befurther
`mipraved. Thereby, the charge / discharge offiency ofthe baltary can be further mapraved.
`{0047} The first sold eleciraiyte maternal may be axnistertal represented by ihefollowing corpasiion famnusa {AB}.
`
`LigansVagghlegCls.eybhly
`
`Foarngla (AS)
`
`where, in ihe campasition formula (48), Me is at feast one selected from the group consisting of Ta amd Nb.
`{0048}
`in addition, in ihe composiion formula (483,
`
`-fx< 8xtOa 8 he:
`..2 (SSS
`0 SRA
`
`SEP eS
`
`Gey s &and
`ix + y}=-8 are salistied:.
`
`foudS] According ‘to the above.
`
`raproved. Thereny, the charge / ischarge afficianey of the battery car: be further hnproved
`
`configuration, the iarnic comiuctivity of thefirst salid electrolyte material can be further
`
`(0G50} As the firs! sold slectrohyte material, for example, Lis¥Xs, LipMQxy, LipFedy, LI (AL Ga, Inika, or LGA Ga,
`ink. can he used
`0057) The first elestroivie layer 101+ may contain the frst solid alectrokde meaiadal as aomein comporent. hi other
`words, the first deciohte layer 1 t-mayinclude the first soll alectrolyte matenal for example, aba weight rato of not
`jess than 50%{not jess than SO%. by weight) with respect in the anhre fiest elacthalyle ayer 11.
`{0052] Accuntingica the above configuration, tie charge / discharge characteristic of the battery can be further maproved.
`{8053}
`in .acitition, the frst-electralyte layer Wi may include, for example, the first solid eiectrolyie material ata weighi
`rafia of notfess than 0%(rot tess than 7O%s Dy welaht} with respeet in the enfire first aiectroiyie layer 11.
`[8654] Accordingic the above configuration,the charges discharge characteristic ofthe battery canbe furtherimpraved
`(0055} The fustelectrohte layer 105 may further. contain inevilatia impunties, The first electrohyte layer 10) may inchide
`ihe starting materials used for the synthesis of the solid stectralvie matenal. The first electrolyte layer TH} may include
`neprodacts of decompasitan products genersted when the solid atectroiyte matetial 6. synthesized.
`fO058] The weightratic of the solid electroivie matetial moluded inihe Trot efectrotyie hyer 10 to the first alectraivte
`layer Ld may be subsiantiaily 1. "The weight tata is substantial1” means thatthe weight rate catoulaind without
`cansidering the inevilable fopurities that may be included in the first clectrolyte ayer 12} is 1, in cther wards, the first
`slectrotyie layer dipray be cormposed only ofthe solet slectrolyte material,
`{0057} Accardingin the sbove configuration, ihe charge /discharge characteristic. of ihe batiary can be further improved.
`[OUS2Z] As descrifead above, the first electraivte layer 104 may be sornposed only of the first salid electrolyte material.
`{6859} The first electrohie layer 1o4 may be positioned withaut ety in camect wih ihe negative alectmde 203.
`{3089} Acces:eee tothe above cantiguration, the electrachemicalbystable second alectratyte layer 102.can be Inserted
`bebween the fh StSpecht|isver Ui1.and the negative electrode 202..For this reason, the contactof the first elactrolyte
`layerctay whiciehis Ukely io fe easily recdijced with the negadive electrode can be sunpressed. As a result, fhe reduction
`cy ttre first nlestoiyte layer 107 can be firther suapressed.
`
`[0004] As the second said electrolyte material, for exarmple, a halcie solid etectralyte, a sulfitesald eleciralyte, an
`oxide solkt efeciralyte,.cr an. organic polymer sciid electrolyte can be used.
`fG06R8) The scoond sold electrolyte matenal may be.a maternal represented by the following compositian formula (2).
`
`LigMYote
`
`Formula(23
`
`where o', § ancdiy are each mmdependently a value. greater than 0.
`
`

`

`EP 3745 518 Al
`
`AP inciudes at least one selected from the group consisting of metaiioid- elements and metal cienrenis other than-Lt.
`»% is at least one selected fromthe oraup-cansisting of C4, Brand}.
`
`fOUSS] According io the abeve configuration, the fonic conductivity of he secand soln electrolyte maternal can be
`further piproved., Thereby, the charge / discharge efficiency of the batiery can be Rurther Improved,
`—8084]
`inthe composition forma (2), AY may include Y inamely, yflriumd).
`{[0065]
`in ctherwords, the second sold elecirahte material may contain Yag the sietal elermend MM’
`Ouse] Accerding fo the abeve configuration, the tonic concdustivily of the second saint eleciraiyie maternal can pe
`further iiproved. Thanshy, the change / discharge efficiency of the baltary can be Rirther improved.
`(O87] The second salid cactruivic matenal may be LisYtl,, LEYBre. or LighBraUigly.
`{8068} According lo the ebheve canfiguestion, the ionic cenductwiy of ihe second sold dectioiie matenal can be
`funtver imoroved. Therehy, ihe charge ¢ discharge afiiciency of the battery can be further improved.
`[6869] The second ¢leciratyie isyer 102 may Include Nie second solid Slectrolyie materiah a5 a main companeat. In
`ather words, ihe second electralyte layer 102 may.inclide the second satid electratyle maiadal ata weight satie of, for
`example, notiess than 50% {natiess than Sik by weight} with respect tothe entire second efectrosyie layer 12.
`{O07D}) Accardingto the shove configuration, ihe charge / discharge characteristic of ihe batiery can be further improved.
`{O07 1] The second éiectrolyte layer Hi? may include the second solid electrolyte material far example, al a weight
`ratic af, farexampie, notiess than 70% inatless than 70% byweight} with pessectiathe entire second elactrohte layer TQ.
`{GOT2} According te the abowe configuration, the charges discharge characteristic of the battery can be further improved.
`(Orsy The sesond clactubis layer TO2 gwiay further conian imeydtabicimpurities. The. second eleciraiyte iayer 102
`can inchide the starting materials used forthe synthesis of the solkt elsotralyteé material The elentrolte bayer 102 may
`include by-producis or a decompasition products generated when the solid eiectrolyie material ts synthesized.
`{074} The weight ratie of ihe sohd electrohave maternal inciaded in ite secend eleciralyte Jayer 102 ta the Aesone
`electrolyte layer 122 may be substantially1. “The weight ratio is substantially 1means natthe weight ratio calculate
`withoud considering the inevitableimpurities that may be included hive secandelectralyte tayer 102 is 1. in. oftner words,.
`ihefret alectrofyte fayer 1O2 may be composed only of the solid electratyie maternal
`{8875} Accordingic the above configuration,the charges discharge characteristic of the battery canbefurther improved.
`[O876} The secand alectrohte yer dog? may be camipased only af the secand-said alectmivie material
`fO77} The firstelectratyie layer 10) andthe second siectroiyie layer 102 may incdude Iwoor more Kinds ofthe materiats:
`described as ihe solid eleciraiyie madenet
`OUTS] Thetotal thickness of the first alectraivie layer 104 and the second slectraivie layer 102 may be hot tess ian
`+ pm. and not morethan S00 piv. ithe total thickness of the fist electrolyte layer-dQt and the secondeisciralyte isyer
`1O2%s less ihan Td wim, the pussibility that the positive elecirade 201 and the negative elactrode 202 are shnorivircuited
`increases. in addition, f thetotal thickness of the frst alecteohdte layer 104 and the second electrolyte layer402 is more
`than SOUpo, ti may be dificull to operate ata high output.
`{6873} 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,
`positive clactode actwe material parties 244).
`{8080} Examplesof the postive electrode active material indicts:
`
`os &
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`ta
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`ag
`
`aG
`
`ithhem-coniaining iransilion metal oxides. fior example, LUNICOADG., LHNICOMN Os, of LITeGs)},
`fransition metal fhiorkies,
`pofyanion matenats,
`fluorinated palyacdion materials,
`transition roatal suliies.
`transition metal oxysulfides, ard
`fransition metal oxynitides,
`
`IN particular, ta itiiuni-conteining transition metal oxide is used as the positive slectrode active material, the
`fOuS4]
`cost raduction is performed and ans aversge discharge voltage can be raised.
`P0082] The positive electrode Al may include a sald electralyte matenal. Accarding to the above configuration, the
`HII fon conductivity insiie the positive elecirade Pit is nersased to allow the operation ata high outpul:
`{8083} The solki sieotralyte material may Include. a halkie sald slecirolyte, a sulfide soli) electrolyte, an oxide satic
`eteciraivte, a palyraer solid slectrotyie, or a carplex hydride salut siectmoivie.
`{0084} As the halide said electralyie, oc eaxaniple matenals exemplified as the first sold eleciralyle material used for
`ine first dlectratyie layer Th] may be used.
`
`fO0S5} As the sudfide:sotd pleciroite, for examals, Ligh-Pads, LipS-SiSg, Lip-HySs, LIS-Gea?,Bs pastyaro75o4:
`Of LinnGeF'y5yo may be usedin addition, LN (4. F, Ch Br, 8, LisMg. LUMO, IM: anyvot Po, 8B: 13a, in, Fe,
`
`

`

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`2nj gp, qonstural nimber may be-used.
`{0O88} Examplasof the oxide solid etectrotyie inchide
`
`EP 3745 518 Al
`
`NASICONsolid olactroivie auch us LITighOgis and its element substitution,
`
`3 porovekite sotd electrolyte such as CLaLytiOs:
`
`a LISICONsolid chectraivie suchas Li ytriseOye, LighiOy, or LiGeDyand ils element substitution:
`a gamet solkt electrolyte such as Lisla.ZroO 9 and is elermeni subslitistion;
`LEN ands H. substitution,
`LigPOy and its. N substation:
`ass to which LipSQ, oF LinCO, has been added using a LL-B-O compound such as LIBOsor Ligh. as fhe base
`theresk card
`qESS cerarnics.
`
`[G087} As the polymer Satid-electrolyie, farcexample,.a cormpoeund af a-pokuner compound anda tthium salt cad-be
`used. The polymer compound may fave anceihylene oxide SUSHI. Since the solid polymer vlectralyie having an
`ethylene oxide sirusture can inchide 3 larae artount of ihigmse eeionic conductivity can be further increased. As
`thefithium sait, IPF, LIBFy LiSbF,, LIASF_; LIGOgCFs, LiNISOSCE: 3. LINTSDoC5Fato, LINTBUSCFaNSCoGigh, OF
`LENSOsCF4),0a6 be used. As the libhim. sail, one dithiurn saltselecteda these may be used aioe. Attemativaly, a
`
`
`mixture of byGoormiare iihiurmn sails selected from-these may be used as the Hin salt.
`{8088} As ihe comes hydride sold siectrolyie, far example, LIDHaLif or LIBg-PoS, can be used:
`
`{0088}. The thickness of the postive elecirade 20) may be nol less than 10 pam and not more than 590 pr. F the
`
`thickness of the positive slecirade 201 is less iran 10 pm, it may be dificul
`to ernsure‘an energy densify of the battery
`sufficiently. ig addition, ¥ the ihickness cf the positive electrode 207 is more than. 506 wim, & may be difficultto aperate
`abe high cuiput
`
`
`peas The pasiive eisctrade active material may be coated. As the coating material, a reternal having low electron
`sonductvity Gan beused. As the coating material, an oxide maferial-or-an aside salid olectrolyte can be used.
`9094) As the-oxide material, for exampin, SiQ>, AlbOg, Tig, BoD, NigCs. Wy, or Zi, can be psa.
`{6882} Exampies of the oxide sold efeciraiyte inciuvie:
`
`Li-Nb-G compounds such as LINDO.
`L-B-Ocompounds suchas LIBG, and LIBRO.
`LLALO compounds such as A(AIO3:
`1:-S-O compounds2schaSLie“LysOq
`LSC conipaurids Su
`Gey
`LiTO compaunds stich &8S LigMsQys,
`Lidscompounds such as LisZrO,,
`LiMo-O compounds such as LisMo0s:
`LAC compounds such as LiveO. "and
`LiO.compounds such as biWo,y.
`
`{6093} The oxide solid slacirolyie has. high ionic condauctway and bigh Highpotential slabiity. Tirerefare, the charging
`i discharging efficiency can be further improved by using the exe salid alectraiyte.
`f08d} The negative elecirade 202 includes amatenal having & property of sieving and releasing metal jons (for
`example, iihtum ions). The negative ciecirade 207 includes. a negative electrode active material for example.
`fOOSS} A metal material, a carbon material, an oxide a nitde,.o fn conound, oy 4 Silicon compound canbe used as
`the negative clectrade active material. The matal material may be 3 single metal. Atlernativel. the smetal material may
`bean alioy. Examples af the metal mater! inchinte fithiim moetalvuand ittium afiay. Examplesaf the canan maternal
`include netural graphite, cake, granhitizad carhon, carbon fiber,
`
`garbon. From the viewpoint! of capacity density, silicon (88, fin (Sn), & siicon compound, or 4 fins compound can. be
`prefersity aced.
`f0096] The negative clectrade 202 may inchade a sald electroite matenal According fe the above configuration, the
`Hihaim. ion candustvdy gisideite negalve electrade 202 is Increased to allow operation ata high outvat. As the salid
`electrolyte material, amatenal hai may be includedin the postive elactrade 204 ¢may be used.
`fOHS7} The median diameter of the negative electrode active material particles may be notless than Oct gm-and not
`raove than POO pin. ¥ the median diameter of the negative elecirade active material particles is less than Ul} pm, the
`negative elactrode active msterial particles. and the solid @lectroiyte. material are not wall dispersed in te negative
`
`electrode, so thal the change / dischargecharictenstic of the battery maybe lowered. In addition, # the median ciameter
`ofthe negative electrode active materiaparticles is more than than 100 gin, the Whiurd diffusion rate in the neuative
`
`:eecarbon, artificial graghie, arat srrorptous
`
`

`

`os &
`
`ta
`
`ag
`
`aG
`
`EP 3745 518 Al
`
`slectrde active mates particles may be loweredAs a result, ii may be dificult in operate the baflery af & high outog
`{8098} The median diameterofthe negative electrode activeyimtertal particles may he larger than the madiag diameter
`ofthe. saciid alectrohte material. Thereby, the negative.clectinde achye matarial partioies and the solid electralyte material
`gan be wall dispersed.
`{809893}
`inthe segstive aliectode 202, 4 volume ratio Vn ragreseniing 3 yaiunie ai ihe negative electrode active matadal
`particles to fhe tofal volume of the negative electradeactive matenal particles and the add electralyie material may be
`neiiess than 3 Sand notsore than 0.55. ifthe vdlume ratio Vinis less tian 0:3 iiriey be difficult in ensure an energy
`isensity ofthe battery sufficiently. On the other hand. #the valume ratio Vinis more than 0.95,it may be difficult to operate
`(04OO} Phe tckness of ihe negative electrode 202 may be natiess Inan 10 grm-and mot more than 300 ura. if the
`® bathery at a high output.
`thickness of the-negative elactrade is jass than 19none tomey be dificull Io ensure an energy density of the tettery
`
`we eiemrode is more har oti} ao, if may bedifficult io operate at
`
`sufficiently. In additiam, if the thickness of the
`high opal.
`
`eOY] The firsi electrotyte layer 101 and ihe second elecirolyte ayer dO2 may aichide @ sulfide sald aleckolyte. an
`
`xide solid elective. a poalymer.aciid slectroiyie, and a carmptey hydride sotich ateciralyte for the purpose of increasing
`ion nanduntvily. As these sald electrolyte materiais, materiais het may Se inchidedIn the. postive electrode 203 may
`heused.
`
`[0302] Al least one af the positive slactade 201, the fist electrolyte layer 107, the secandelectrode layer 102, and
`ine negative slectracde2028 mayinclude = binder for fhe purpose of improving adhession behween ihe particies. The binder
`used m order io improve the Dinding sroperty of the matenat which forms the electrade.
`{0793} An example of the meterial of the binder is poly(vidylidene Nucnide} cohdetrafuoroethyieng, palyethylene.,
`polypropylene, aramid resin, polyamide, polvirdicde, polyamideimide, palyacrionitrie, polyacrylic ackt, metpalyacr-
`ylaie- esterety) palyacrviate ester, hexyl polracnlaie ester, palymethecryic acid, methyl palymethacryiste ester. athyi
`polymethucrylate ester, hexy! palymethucrylate esiar, polyviny! acelufea, paryvinyipyoalidane, polyether, palyethersuyl-
`fone, hexafunrmopelyorapylene, styrene bulaciene nubber, or carbaxyrmethyicellulose
`[0484] As ihe binder, & copolymer of two or more kinds of materials: selected fromthe qraun consisting of telraRuar-
`
`oethylene, hexafluomethyiene, haxafluoropropyiene perfluaroaiky! vind ether, viniidene fluoride chiorabifiuarcealty!
`ene, aiindene, prapyiend, Geniafluerosrapyiene, Haoromethyl vinyl ather, acrylie acid, and hexadiene cad be ased. in
`addifion, two or more kinds selected from these may be mixed ancd.usedas a binder.
`f105) At isashone of the postive elactrade 201 and the negative elachide 202 may iiciude & conductive agent for
`the purpose of noreasing the electronic conductivity. Exammes af ihe contiuctive aqent inctude:
`
`graphite such as natural graphite or arificial graphite:
`carbon black such as acetylene black or keen. Bleck:
`e aonductive fiber such a9 4 carbon ther or a metal fiver,
`
`carbo Ruoride:
`metal powder such 8s ahiminant
`conducive whiskers such as. zine oxide or potassium. thanate:
`a contective rested oxide such as fteniun oxide! and
`
`a conductive polymer compound such 3s polyaniline, sotyoyrrafe, or polyibionhene,
`
`fOIHS] Cost reduction can be achieved by usmg a carsan conductive agent s48-1572 conductive agent
`{O3HF} The pusilive shecirode 201 may widludethe first solid ciacitrofyle maternal.
`fFe188]) According in the above configuration the ionic conductivity between thea positive dectrode 201 and the negative
`electrode 202 can be further improved.
`[O3O9} FG. 2 shows a cross-sectional view al a Dallery TTI id the frst ambarniment.
`{OTTO}
`In ihe battery THO accarding ta the frst ambadiment, the positive olectradle 2th includes 8 jruxect matertad at
`
`first add eiectralyie parinies 374 and the positive slestrode active maternal patictes 274,
`(Ot44}. The first solid electrolyte particles 117 are particles formed of the first soik! electroiyie matenal, ar particles
`including ihe first actid electraiyle matenat as a mein camponent (ior example, al aoweight rmtio of nat less than 50%
`fnuf jess than 50 by weight Yo) with regard fo the entire first sold-electrofyie particles 711).
`{O142)
`in additinn, the shape of the fest solid clectraiyie particles 777 is. nat limited, and may be, for example, an
`acicular shape, 3 spherical shapeor an eiliptical «phencal shage. For example, the shage-af the first solid plectralyte
`panicles 11? ypaay be paniculate.
`0713]
`For example if the shape of ihefirst sotid elactratylie particles 111 in the first eribadimmeant is particulate (or
`example, spherical), the median diamefer miay Ge mot more than d00- urd. ihe median diameter is more than 100 am,
`
`
`the positive electrode active material particles 21) and the first said elactratyle particies T}1 armnal dispersed well m
`ihe pasitive electrade, sothat the charges diacharge characteristic.of the battery may be lowered. In addition, im the first
`
`

`

`EP 3 745 518At
`
`embodiment, ihe median dianieter of the first-solid Glectrniyie padicies 721 may be nat more than 10 ant.
`{0t74} According to the abcve canfiquration, the pasitive electrode achive material gadicles 271 and the first satid
`slecifabte particies 1] 1 can be disnersed wellin the pasitive electrode 207.
`oid]
`inthe firstembodiment the median diameter of the first salid electrolyte parities 111 may be smater than the
`median diameter afthe cositive electrode active matenal particles
`214.
`
`fO978} According to the above configuration, the firsf-solid'seleoftote particles Th ane the postive electrode active
`
`material pacicies 21) can be further. dispersed wellin the electrode.
`{O117] The median diameter af the pusilive eleckade active maternal particles 271 ray be not less than O.] pm and
`notmore than 100 gm. H ihe median diameter of the positive eieclrade active maieral particles 271 is bess than than
`0.4 pm, the pusiive electrodeactive matenal garficles 24 t and the first scielactroiie particles 114 are not dispersed
`Wellin ihe postive electrode 30) and thus the chatge / discharge characteristic of the battery may be lowered. in
`addition, F ihe median drimeter af the positive electrade active oiateria! particiss 21) is. mare than TOR am, itil
`diftusior: in the wostive ekacirade active maternal particles 2} is rece shew. As a resall, Remey be difficall ta aperate
`the battery ai a iigh aptput.
`fOt18] The median diameter of ihe pusifve efactrode active matenal particles 244 may be larger than the median
`diemeier of the fest solid electrolyte particies 171. Thereby, thepositive electrode actwe material particies. 271 and the
`
`first solid electrufie panicles 341 oan be well dispersed.
`[8378]
`in addition, ihe positive slectrade 204 may Include a plurality of the first solic alestrohde paridies TT} and a
`plurality of ihe positive electrode active matenal particles 271.
`{G20}
`in addition, in the positive alectrade201, the content of the first solid Glactrulyfe panicles. 11 may be. the same
`@s.ar diferent fram ihe cantent of the positive eiectrode active material panicles 244.
`fOi27]
`inthe positwe clecinode 701, a volumeratio Vo represeniing a yolume of the positive ciectrode active material
`
`varticlas 21} to the total volume af the postive slectrode active material particies