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`EP 3736 834 Al
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`EUROPEAN PATENT APPLICATION
`published in accordance with Art. 15344) EPC
`
`(43) Date of publication:
`49.41.2020 Bulletin 2020/46
`
`{24} Agplicdtinn number (888e9g3s.4
`
`(22) Date of fling: 17.12.2018
`
`{B4) Designated Conracting Sistes:
`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:
`BA ME
`
`Designated Vatidation States:
`KH MA MD TN
`
`(30) Priority: O6.D4,.2078 JP 2a7ened4d7s
`
`{71} Applicant Panasonic intellectual Property
`Management Co., Lid.
`Osaka-shi, Osaka 840-8207 GIP}
`
`(72) inventors:
`* ASANO Tetsuya
`Osaka-shi, Osaka 540-8207 (IP)
`
`io RECT:
`net
`HOTB 1/06 2OROD
`CHG 990 HOF
`CONG 25/06 BOAT
`COG savageen
`HOIM a7eg 200800
`HORM TOMES AON
`
`COT 17/09 een)
`COG FH206}
`COTE 29,00 250
`core peaseT
`HoIM toreseg GFO07
`HOM tovoseaon
`
`interna onal application number:
`PCT/JF204 8046258.
`
`}
`
`infemational publication numbec
`WO 2079435343 {11.07.2019 Gazette 2019/28}
`
`SAKAI Akibira
`
`Osaka-chi, Osaka 540-8207 WIP}
`SAKAIDA Masashi
`
`Osaka-shi, Osaka S$40-6207 {IP}
`NISHIO Yusuke
`
`Osaka-shi, Osaka 540-6207 {JP}
`MIYAZAKI Akinobu
`
`Osaka-shi, Osaka 540-9207 {JP}
`HASEGAWA Shinya
`Osaka-shi, Osaka 540-6287 (3F}
`
`4) Representative: Grinecker Patent- und
`Rechissnwalte
`PartG mbes
`
`Leopokistrafe 4
`80802 Munchen (D6&}
`
`
`
`(84)
`
`SOLID ELECTROLYTE MATERIAL, AND BATTERY
`
`Asolid slectohde matstial according to aa as-
`{67}
`pect of fhe present disclosure contains Li Y, abieast one
`selected tram the group consisting of Mg. Oa, Sr, Ba, Zn,
`Sc, La, Sra, Bi #e HE NBend Tr, and af least ane se-
`tected fram ihe grouconsisting of Cl Br andl An x-ray
`diffraction patiem of the solid electrotyte material ob-
`tained. by using lu-Ka radiation as ihe X-ray soiree in-
`cludes peaks within the .arige iq which the -difitaction
`angle 24 4s.25° ar more and 35° or hess and incindes ‘st
`feast ane peak within the sarge by awhich thediffraction
`angle 20 18 43" oF pore land OS)oor less.
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`EP3736834Al
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`Prrted bydouve, S50} PARIS (FRE
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`Description
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`Technical Field
`
`MOOI] he present disclosure relies fo satid electratyie matenais and batteries:
`
`Background Ad
`
`0002] PIL } discloses aq all-saiid-stale battery made with a sulfile solid ciectmiyte.
`
`MPLA discloses LLYCI,
`NBL 2 discloses LLYEr,.
`
`Citatian List
`
`Patent Lteratuce
`
`{6603}
`
`PTL +: Japanese Unexarnined Patent Application Fuudication No. 2044 - 128332
`
`Non Patent Literature
`
`fOuG4]
`
`NPL2. Anorg. Alig. Cham. 82S ¢?907), JO67-1O 73.
`MPL 2: =. Anorg. Allg. Chem. 629 (897), 1352-1358.
`
`Summary af lavention
`
`Technical Problera
`
`O05]
`
`in the related art, is hoped thata solid electroivie material highly conductive fo Hihjum ions wil be realized.
`
`Solution ta Problen
`
`fOuOe] A solic electratyte maierial in-an aspect of the present disclosure is composed af Li, Y > af bastone selected
`from: the groug consisting of Mg. Ca, Sr Ba, Zn, So-ta, Sm, Bizy, Hi, Nb) and Ta, and at least ode selected fromthe
`group. consisting of Cl, Br, and Lan X-rey diffraction paliers of te sold alectnolyte material cbtained by using CuKa
`Tadiation as ihe M-ray scurce includes peaks. within the range in which the diffraction ange 204s 25° ar mare and 35°
`oripas, anctinchides stleastone paak within the range iq which the diffraction angle 28 is 43° of more and 51° or jess:
`fOUOT] A said slectratyie maferial in an aspect of the present disclosure is composed af Li, Y afblastone selected
`from. the group consisting of Mg, Ca Sr, Ba,2n, So, Ua, Sm, Bi Zr, Hi, Nb, and Ta, and at least one selectedfromthe
`group comsisting of Cl, Gr, and}. A first.canveried patter, which is obtained by measuring an x-ray diffraction pafiem
`of the solid electrotyie material by using Cu-ka padiaion as ihe X-ray source and converting the N-ray diffraction paftem
`io change Hs forzanial axis fram the diffraction angle 28 toa, where.q = bxsinG, whare 4is the-wavetength of the Cu
`Ke radiation, Includes i base péak within the range in whieh.q is 1.78 A? or mere and 299 Arbor fess. A second
`eanverted palten which is obtained by converting the X-ray diffraction patiern ta change ds horizontal axis From the
`diffaction angle 48 fo Giga, where gg is the q Gurrespanding te the base. peak in the rst converted patiern, includes &
`peek within each ofthe range id whieh qigg is 1.14 or monsend T-17 orless and the range in which aijis 1.62 or more
`and 1.85or less.
`
`Atvantagecus Effects of Invention
`
`{8008} According tu the greseni.discingure, sold electrolyte materiais highly conductive ta Aitiur ions -are restized.
`
`Brief Description of Drawings
`
`[8009]
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`iFig. 1] Fig. 4 is 4 cross-sectional diagram that ihusinafes a schematic structure ofa battery in Embadiment 3.
`{Fig 2] Fig. 3 is 8 ciagrarn Hhisirating peak paiterns BYARD.
`{Fig. 3} Fig. Fis clagcamHiusirating canveried paiteme:
`iFig. 4) Fig. 4 is a schematic cladram Nusirating a method for testing for ionic canduchvity.
`fFig..O] Fig..5 is 8 graph shistrating fhe results of a test for ionic conductivity by AC impedance spactrascapy:
`iFig. G) Fig. Gis a graph shustrating wilial discharge characteristics,
`
`Deseription of Embodiments
`
`fGO78}
`
`ithe following, entbodiments of the present disclosure. are diascribed with reference to drawings.
`
`‘Embodimentt}
`
` A.salid eiectravie material in Embodiment (is amaienal composed of Lt ¥, MM, arc.
`{G044}
`fG072} Mis aljeast one sefacted from fhe qroup cansisting of Mg, Ca, Sr Ba. Zn, Se. La, Sm. Bi gr, HE Nb and Ta.
`feO73]
`Xis atieast ane selected fram the group consisting of Ch Be: and |.
`16044] An X-raydiffraction patiern of the solid dlectralyte matenalin Embodiment 1 obtained by ising Cu-Me radiation
`as the x-ray source includes peaks within the range inwhich the difiraction angle 20 is 25° of more end 35° oc less, and
`includes at leastone peak within the range in which ihe diffraction angie 22 is 43° of more and 454° or fess.
`{0415} This comiquration helps realize a hakde said electrolyte material, which is a solid electraiyie material highly
`conthective te Hiiium ions.
`
`fOO78] This configuration, furthermore, hele realize an al-solic-state secondary batiery superar in charge and dis-
`change characteristics tirapgh the use of ihe saidelactralyle material in Embodiment 1.
`fOOTF] Through the use of the solid electratyte material in Enibudiment 7, nioreoyer, a sutturfree al-solad-state sec-
`ondary batiery is malized. That is, ihe -coanfiguation of the solid electralyfe maternal in Ernbodirment 1 is net one ial
`produces hydraden.sutide when exposed to the ai {e.g., fhe configuration in PTL 7). The use-of the material therefore
`Reins realize an. at-sdid-state secondary battery tat produces to hydrogen sidide aad therefore is superiorin safety.
`{[O018} The X-ray ddfractian pattern of the solic eleciraiyie matarialia Embodiment 1 mayinohide twopeaks within the
`Tange in which the diffraction angie 20 is 56° ar more and 85° or fess.
`8078)
`FAis configuration helos realize & solid eléciralvie material more conductive fo Whim ions,
`fOU28] The X-ray difraciion pattern of the salicl etectralyie material in Erabadimeant | may include a peak within the
`range in which the diffraction angie 26 is 72° or more and 18° or fess.
`£0024] This configuration helps realize a salid electralyte materist more candisctive to ithions:
`{0022}
`8 should be noled thet there are two peaks within a geriouwar range(ecg, ihe seange in which the diffraction
`angle 28 is 3S of more ayid 25° of leas or SO" or more and 83° of jess)" as staied herein inckicies fhe meaning that
`“there are bye distinctive peaks within the particular range.”
`{0023}
`“Distinctive” rieans thal when the positions of the iwe peaks are defined as 28, add 20, andthe full widihs at
`half maximum as. JAG. and 2A05, at least the fallowing is salisted: 1205-284} > (2AG, + 2AB5).
`fG024} The acid elactratyie matenal in Embodiment i ray include a first crystal phase. An axarnple of acfrst crystal
`phase js a crystal phase that gives 4 characteristic diffraction patiern as described above.
`{025}
`if the measured infensdy is cot sutficeniy high, the patlem maylack a sttisel of ihe peaks.
`fO026]
`Afirst crystal phase that gives a characteristic diffraction diagram as desorbedabove s nat incited fo a particular
`crystal structure, bufexamples inmkaie crystal structures jike-those described bejow.
`{0027} One is. stucture a which ihe anton sublatiice Jramewark is @ cubic close-packed (face-cantered, cutic) oc
`distoried cubic close-packed acecentered cubic} aiamic airangement Thad is, if an anion sublattice, each anion is
`coorndtieted ta by hwelve offer anions. The mierior anaies ai the triangia farmed by the closest hwo pf these twelve anians
`ane ihe central anion are all aporiximetely 0° More speciically, the intener angles of this dangle fal wither tie range
`ol approanmetely OO" 25°.
`jOU2R} An exaraplc.of such 8 structure is ihe Li,ErBr. (ereinafier aise denoted as LEB) system, which has a crystal
`siruciuce iket belongs te the space group C2/m_lisdeiadedatomic amangementis found in the lnormanio Crystal Struckwe
`Database CSD) GCSNo. 50182). Other examplesinclude sainel and inverse spiney structures, which belong tea the
`space group Fd-3imi, imma, eis.
`{8029} The sdiid ciectroiyie materalin Embodiment } may nclide an extra crystal shase,@.crystal chase that has a
`orysial structure that is not adirst crystal phase.
`(0030] This configuration helpsremtize a solid electroiyie material mare canductive tatithium idns. Specifically, ii'searrs
`that whentte solid electralyfe material iss. a-crystal structure ke a first crystal phase, anions are alvacted ia the yicinily
`of Yoor M more strongly, and at the samefine Mand Y are mixed logether, cheating regions in whichihe patential of Li
`ions is unstable. This creates a paihway for lithium ions fo dvfise through. The Livieplieted compasition, moreover,
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`means that unoccupied stecs} is created, meking he crystal more conductive fo fifaim ions. As a resulf, the inventors
`
`believe. ihe materials. Rhhen fon cormekmivey is further miproved.
`{8031} The salid aiectotyie material in Embodiment 1, nioreaver,.can Ge in any shape, such as acicular, sphedcal, of
`elipsorial. For example ihe solid electroite material in Embodiment | may be particles: Muttiie panicies. may be
`stacked endthen compressed ta foampellets or sheets.
`§0032} Wihe solid electraiyte matetial in Envbodiment | has. a particle shape.ie.g., apherical), its median diameter may
`be 0.1 prioemore and TQ] war oriess.
`{OU32]
`in Erabodinent 7, furthecmore, ihe median diameter may be 0.5. pamar more and 10 pm ar fess,
`[0034] This configuration helps. further imorease tanic canductivity, and also allows the solid alectrotte material in
`Ernboadcimant tT to jenna better dispersion state, for examale with an active material
`{0035}
`in Eathodiment 1, furihennore, the solid electrohte material may be smailer than the median diameter of-an
`active maternal
`
`[6036] This configuration allaws thesolid oleciroivyte misterialin Embodiment dio doora beller dispersion. stata, for
`exzerople with an-achve material
`
`fEmbadimert 2}
`
`in the following, Embodiment 2 is described. Any detads that fraivealready teen deserted jn Embodiment 7
`{8637}
`above are. .omitied where sopropriaie .
`{0038} Asolid electesiyie material in Embodinierd 2 is 4 matenal composedof Li, YY, M, and.
`{0039} Mis atleast.one setacied fromm tie qroupconsisting of Mo Ca, Sr, Bs, Zn Se) ba, Sm Bi Zr Hi-Nb, and Ta.
`fOUda]
`Xx is at least one selected from the group consisting of Ch. Br, and a
`{G044} AAiest converted patlem, which is cbtgined by measuring ad. X-ray difvaction pattem. of the-solid electrolyte
`raaterial in Embodiment 2 by using Cu-Ke, radiation as the X-ray.sauree and converting the K-ray diffraction pattern fo
`change @s horizontal axis from the diffraction angle 28 io q, where q = 4rsing’s, where 2. is the wavelpagth ofthe Cu
`Ke radiation: includes {6 tase péak within the range in whiehq is 1.78 A? or mere and 249 Actor less. A second
`eanverted paltent which is obtained by converting the X-ray difvaction patiern. ta change ds horizontalaxis from the
`diffraction angie 23 to afqyg. where dg is ihe q cowesponding te the base poak in the fest converted pattern, inchMeas. a
`peak within cach of ihe range in which q/gyis h14 orrore and To)7 or less and the range in which g/d,ts Taa.or more
`and 1.65 of tess.
`
`fOUd2] This contiguration helps realize a halide solid sleciroiyte matensal, which is a said oleciraivie material hahh
`conductive to lthkic aus.
`
`f0043] This configuration, furthermore, helps realize an all-solid-state secondary battery superior in charge and, dis-
`charge. characteristics through ihe use ofthe solid electrohte material in Embodiment 2
`fOO44}
` Throuch ie.use of the solid electrolyte materiaf in Embodiment 2, moreover: a sulfiy-irgeali-caint-statesec-
`andary battery is: realized. That is the cenfiguratian of the solid alectrohte matedal in Embodiment 2 is not ane thet
`produces hydrogen suiide when exposed to the ay (e.g. the configuration iq PTL.1). The useof the material ihereiore
`helps realize an aif-salid-state secondary battery that produces na hydrogen sulfide and therefore is superior in safety.
`{0045}. The sconond corveried pattern mayinclude a pack within each of the range in which gfq,-is 4.88 of more-and
`44 or fess and the range in which g/g, is 1S or more and 2.1 ar fess.
`{6046} This configuration feips realize e saikt electrolyte material mare cariductive to Ithiuim jon.
`{8047} The secondconverted pattern mey inclidea peak within the rangein whichaqeis G48 or more. and 6 5G ar less.
`fG048} This configuradion helps realize a soit eleciratte matenal more conductive to Whim nits,
`{0049} The solid electratyie maienstin Erabodiment 2, as in Embodiment, mayinclude a first crystal phase.
`
`oh
`
`fO0USHy] An example ofa first crystal phase is a trystal phase that dives a characteristic converted ations ws describe
`
`above
`
`if the measured intensily is not sufficiently high, the pattern may hick a subset of the peaks.
`M054}
`{0053} The solid cisciralyte maferial in Eribadiment 2 may ticlode an exits crystal. chase, 3 coystal phase that
`erystel structure that is nota first crystal phase.
`[6053] The notation "the range in-whieh partiowar parameter A is value & lo vehye O° hereinrefers fe “the ranged
`whieh "Gs Asc"
`
`hes a
`
`AMathodfor Praducing a Salid Electalyte Materiaic
`
`{0054} A solid ciectialyie malorialin Embodivient } or 2 can be produced by, for example, the folowing metho.
`P0085} Hawonateral powders of binary halidesare proparedfo give the intencied consitutive slements. For examaie,
`Pa sold elactratyfe matadat that contains La, Y. Sr, and-Br is produced, LIB, YErs, and Sriry arcorenared, By selecting
`ihetypes of fhe faw-matenal powders, fhe anionic compostion can be determined. After ihe raw-matenal powders are
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`mixed together wall, the raw-material powders are nuked, milled. and allowedfo react by the mathod ofmechanachemion!
`milling: The nibture may then be fred ia vanuun of inert atrosahere. Atametively: the raw-material powders may be
`lived dy me Vectann or inert almosphere after being mixed together well The firing candiions can be. for example, 4
`temperature within ite rande of TOC ic Ga0N? and al least 1 four of fining.
`f!OS6] This gives a sold electrolyte matenat that inchideas a composition as descibed above.
`PO057} The types and crystal structure of crystal phases in the-salictt material and the positions of peaks in the X-ray
`
`diffraction pattern using Cute as the radiation source and in converted patterns can be detennined by adjusting the
`percentages of rawmaterials and customizing the method and parameters for ihe reaction behyeen the raw-material
`yrow'ders.
`
`fEmbadhvent 3}
`
`in the following, Embodinient 3. is described. Any deteatis that have already been. decerbadin Embodiment 1
`{0058}
`ara above ree ornitied where spprapcdate,
`fO089}]
`Abattery in Ermbedwnent 345 made with a solidelectraiyte maternal descrifed in Embodiment f or 2 above.
`{8060} The wsttery in Embodiment 3 includes a sotid electrolyte malaga! a pasitive alectrode, a negative checirade.
`and an-elactroiie layer.
`[8664} The eleciralvte layer is a layer placed betwaen the positive and negative elecircades:
`{9082} At least one of the positive ehectrode. slecitraiyte layer, ard negative electrode coniains a soint electraiyie
`miaterial in Embodiment tar 2.
`
`{0063} This configeration helns biprove the charge and discherge characteristics af a palany.
`fO064]
`in the folluaving, & specific axaniple ofa battery in Embodiment 2 is desenbed.
`{065}
`Fig. 1 is a cross-sectional dmigram thal dustrates a scheniatic. stucture afa-baiieny 1900 in Embadiment 3:
`8086] The battery 1000jn Embodiment includes a positive electrade 204 anegative electrade 203, and anelactrafyte
`ayer 203.
`fOU67} The postive electrode 201 contains positive electrode active material panicies 204 and solid electrolyte panichss
`108.
`
`(0068} The Sieciroiyte layer 202 is placed behween ihe posite electrode 201 ard the nedalive electrode 203.
`{8060} The elecirdivie Inyer 20? contains an electrolyte material (e.g, a solid clactruiyte material,
`{O07} Fhe negative electrode 203 canidins nedstive electrode active metenal particles 2045 aret solid sleciralyte
`peaticies 10.
`{G077}] Thesold elecirciyte particles 10 are particles of a solid electolyla material i Embodiment 1 or 2.or particles
`ifat conlaim a solid slectrofyie muferial in Embodimentor 2 as thei primary ingredient.
`{O072} The posiliveslertrade 20% contains a. matenal thal has. atendencyto-siore and. release meatal ions (e.g. Hihurn
`ions}. The postivedlectracde OY contains, for example. a posive electrode active raterial (6 q.. positive electrade
`active matetat particies 2044.
`{0073} The pastive electrade active meteral can be, Tor example, 3 lithium-coniaining Iminsition metal oxide (e°¢.,
`LENICOAD., Ur LiCads), & transitun metal fluoride, a polyanicn or fluoringied polyanion material, a transition metal
`sulfide, inimaition metal oxinende, a pansition metal oxysulfide, ofa transition metal oxynitride.
`[O074] The median diameter of the positive electrode active matanal paricies 204 may be O.1 pm or more and 106
`pitt ariess. Hothe median diameter of the positive clactrade active material particles 204 Is emailer than 0.7 jum, the
`positive dectrade active malenal panicles 204 ancthe halide solid: ciectrolyie material can fail io forma good dispersion
`slatein the positive electrode. This afferts the charge and discharge characteristics of he battery. the median diameter
`ofthe positive clectrade active matenal pacicles 204 is larger than T00 pm, bthiuen diffusion inside the posilive elecirade
`active mafanal pariicies 204 ig slow. High-power operation of the batten, can therefore be difictat
`[O875} Thernedcian diameter of the gositive clectrode aclive matanat Gortinies 204 maybe lacgerthar thai ofthe halide
`Soha electrolyie material. This ensures the positive electrode active material particles 204 and ihe halide. sald clectratyte
`maiedal wit forma good disgersinn Stata.
`fOO78}
`For the ratio by volume belween ihe positive electrode active maternal particies 204 and thehalide sulid eiec-
`trohte material "wv100 - v" in the positive elecitade 2017, R may be that 30 < vs G5. Wy <30, can be dificult fo ensiure
`a sufficiently high eneray density of the batiery, iy > Gh, high-power oneration can be difficult,
`the thickness of the
`{0077} The thickness ofthe postive electrode 20) may be TO prior riore and.500 pen ar legs.
`pagilive slecirade 201 is smiaiierthan 10 pen can be dificull to ensure.a sufficiently high eneray densityaf the battery.
`iFihe thickness of the posifive electrode 20] is jarger than 00 pm, high-power oparation nan be difficult
`0078] The eiectratvie layer 202 is a layer thal contains an. electmiytemiatertal. The eleciratyie matedal is, for examute,
`@ solid siectrotyic material. Thatis, ihe ‘electrolyte iayer 202 may he a-salkt aleciralyte layer.
`fO079} A solid electroiyie layer niey contain a solkl siectrolie maiadalin Embodiment 4 or 2 above as ts poimary
`ingredient, That is, a solid electrolyte layer may cantsin a schd-electraivie material in Embodiment] or 2 above pan
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`By
`aid dlectralyie
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`fayer (a0% by weight or
`
`amount of, for example, 50% of more 54 & percentage by weight to fhe whole
`mare}
`0080] This configeratian telus father improve the change and discharge characteristics af ite battery!
`fOU81] A soaik! electrolyte layer, moranver may comiain asad diectrolyte material in Embodiment tor 2 above a aq
`amount of, for exampis, 7Q%. or mare as a percentage by weight in the whole salid electroivte layer (70°86 by wenyht or
`raare},
`fOO82] This confgeralien hers feather improve the charge and discharge characteristics af ite battery.
`{O082Z]
`if should be noled thalasclul electrolytelayer may contain, besides a solid electrolyte material in Embodiment
`i or 2 above as Ns onrmiary ingredieni, Inevitable impunties or starting materials used for the synthesis of ihe solid
`slectraiyie material, by-procucts, decomposition products, sic.
`{G084} A solid slerteoiyte iayer, furthernionss, may contain a sald alectrohie material in Erabadinani | or 2 abovein
`an amount of, for eyampie, TOTas a percentage by weight to ite whale salid etectrolyte fayer (G% by waight
`exchiing hripuities that are mewiehily mixed in.
`{6085} This configuration feips forther improve the charge and chacharge characteristics of ihe batten:
`fOO8S}] A solid electrolyte layer, therefore, may be made satel ofa sotd electrolyte material ry Embodiment { or 2
`{0087} Alternatively, a sold electrotyte layer may be made solely ofa salid electrolyie maiecdal different from thase in
`Embodiment ¢ ar 2. The sald clectralytematernal diferent fram those in Eribodiment tor 2 canbe, for exaniple, Lighg™,.
`LipFex,LA) Ga, Ink, Li(Al Ga inix, Late. (x: Ft Br, ord.
`{G088} A sald elactrotyte layer may cantain a solid electrolyfe material in Embodiment i or 2 and a solid electrotvie
`riaterial diferent frany these in Embodiment | or 2 shove fogether. in thal. case, the bya materials may be dispersed
`uniformby. ibraay be inet a teyerof.a solid electohis matical in Embodimant't or 2. and e layar-cia sold stectralyte
`material differant frony those in Erbogirent 1 or 2 above are arranged jn sequence with respect to the direction of
`stacking of the bailenc
`{0089} The thickness of a salt) electralyte layer may bed pm.or more and 1000 am ariass. Pihe ihickness ofa said
`sleciraiteiayer i smaiier than 7 am, the wish is high af shart-circuitieg between the posilive electrode 201 and ihe
`negalive slecirode 202. f the thickness of a solid clectrojyfa layer is larger than 1000 am, high-pewer operation can be
`difficutl.
`
`. HiRRum
`{0080} The regative slectkode 203 contains a matendal hat fas 4 fardencyte store and release riptal ions (6.9.
`ONS} The negative siectrade 203. contains, fur exampie, a megative electrade active material ie.u., negative electrode
`active matetiet paricies 205).
`OUST] The negative electrode active material can he, for exanwie: a metalic material, carbon material, oxide, nitride,
`tin cambound or sticen campound. Asmretaiic metenalcan be a pire metal. Allernatively, a metallic materiel canbean
`alloy. Examoles of -retalic materials inchidie materials such as ithiint metal and ithiimathiys. Exampies of carban
`matacats include materiais such as5 neeturalgraghite, coke, graghitizing carbon, cerbon fiber, sgshercal carbon, acliicial
`graphite and-arnorphaus carbon. Seinon ‘Si} fin (Sn), a siicon. carmponnd, arin compound may be used for the sake
`ofcatacity geranivolume. The advaniageofcontratied alectinalcdecampnosition sravided by the salid alacbohte matanal
`in Embodiment tar 2 is mare prominentwhen the Negative electrade active reacts ale law average potential.
`{0092} The median diameter of the negative electrode active material particles 205 may boe-Dt wnt or rore.and 100
`pm oF jess. the median diemeier of ihe negative slectrode active material particles 205 Is smetler then 0.1 qm, the
`negative electrode activematerial partinias 205 and the sathd alectraivte particies 100 can fil fo form 4 good dispersion
`state in ihe negative alectrode. This affects the charge and discharge characteristics of he battery. fihe median diameter
`ofihe negative electrade active materia] particies 205 is larger thar: 100 gm ithium diffusion aide the neqafive electrode
`antive material particles 205 is slow. High-power operation of ihe battery can therefore be dificult,
`{0093} The median diermpter of the negalive electrode active material particles 204 maybe largerthan thatof thesolid
`elacirahte particies 100. This ensures the reqative electrode active material paricies 204 andthe halve sod eleciralyte
`Material wil form. a geod dispersicdn state.
`(0848)
`For ihe ratia by volume between ihe negaiive electrode active material paricies 705 andthe solid clectraiyie
`
`pertidies 100 “wcTit -v" in the negative elpctrade 205, may be thet 304 0< 5os ey <030, foan becdificall o-ensure
`
`a sufticientiy high energy density of ihe ballery. Wy > 85, high-power operatian nan be dificull
`{6095} Thethickness of the negative elecirade 203 may be 10 wnmvormore: and 500 ym. ajess: ithe thickness ofthe
`negative siectrode iS amailer than 1G pra, tcan be difieuti fo ensuresufficiently Ainh eneray density.of the battery. If
`the thickness of the negative siectrodeis larger than SOG pro, high-power openaiion can be dificull,
`{8096} At least one of the positive alectrade 20h elective layer 202, and negaiive dectiode 203 may coniain
`
`sulfide Salis electrolyte or oxide suid alectroiyte for iiproved ionic canductiwiy or chemical stability:
`trochemical
`siebilily. Sulfie sald cloctrotyies tat can be used Inclue alectrohytes such as LigS-PaS_, HgS-SiSy, LAS-BySq, LigS-
`
`Bese, Lis9pG@gsgPa gay, AMD LySePySso. Oxkle auld slectroles that can be used include electraly 2
`;
`NASICON said aeciolytes. typified by LITG(POg) anid its subsittuled derivatives, (Lali.dasad perovakiesolid
`electrolytes, LISKCGN solid electrotyies, typified by Ligg2@nGeyty, LigsiQy, DGeOQy, and their substituted derivatives,
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`garmeLbased sond electrolytes, typified by Liglasg#mO,, and ts substitted derivatives, Li,N and fis H-substitulad de-
`fveives, ant LigFOy and its M-substituled derivatives
`{0097} Atleast one of the positive clectrade 201, electrolyte layer 202, and negative electmde 203 may contain.an
`organic polymer solic slectrolyte fay iniprevedionic conductivity. Anorqanic polymer soln elsctrohie can be, forexaranie,
`a compound of 3 cohmer and at least cane iihium sat, Fhe palymer may have the ethylene oxide sinickwe. By having
`the ethylene oxide structure. the polymer can accommesiate more of.ihe lithium salt, thereby helping further incraase
`ionic comduntivity, Lithium sels that can te arsed Include, for example, LIPF,g, LIB, LiSbF,. LIASsg, LISO.CFs.
`UNIS OsCF ais, LINGOsooats, LIM{SOCra SOaCarg) and LIC(SQ,CKr aie. The iihium sal can be one ithiunr sali
`selected from these and ised alone. Aliernativealy. the fittiurn salt can be a mixture of fava of more Jinn sails selected
`from: these.
`
`{0098} Al least one of the pasitive electrode 201, slectolie layer 202, and negailve electiode 203 may contak 4
`nonaquenis liquid electrolyte, gel slecivsivie, or janie liqund for sasiar exchange of hthium ians and improved output
`characteristics of the batters.
`{6089} A ndoaqueous thndd slectolyte contains at least one nonaqueous solvent and atleast ane hmm sali.dissolved
`inthe nonaquecus solvent. Nonaquequs solvents that can be used jnciude suivents such as cyclic carbonate solvents,
`
`Rnear carbenaie salvenis, cyclic eather solvents,
`linear ether scivedia, cyclic esier salvents, near ester solvents, and
`fluermated solvents. Examofes of cyclic carhonete solvents include solvents such as ethylene carbonate, praoyiene
`earhonateand butylene carbanaie. Exeripies of linear carbonate solvents include solvents such as dimefhyl carbanata;
`einyi raeihyl carbonale, ancd.diethyl carboneia. Exampies.af cyctic ether scivenisinchice saivents such astetrahydrofuran,
`Ld-diaxane, and i Soioxolané. Lingarsther saivents include solvents such as 1 S.dimethoxyethana.and 3 o-diethex-
`yethane. Examines af cyclic esier saivenis inciucie solvents sich as y-butyralectone. Examples of Hnear ester solvents
`ingiuge solvents suchas piainy! acetaie. Exanwwes of iyarmated sobvents inchicte salyerds. such as thuorasthyiene
`carbortaie, methyfurercpropiensia, fiucarabenzene, Hucroatty! methyl carbonate and faorodimethyviarie carbonate. The
`nonaqueous salvent canbe. one nonaqueous solvent sefected from trese andused sione. Atternatvely the nonaqueous
`solvent canbe a camtination of hyo ar more nanaguecus sclvenis selected from these. The nanaqueous liquid electrolyte
`May contain at least one Tuarnated solvent selected fram the group consistig of fiuaracihyiene carbonate, metry
`fluoropropionate, Ruorbenzane., fuorceitiy! methy! carbonaie and Nuarodimeihyiare carhodate Lihiim salts ihat can
`
`be used:
`inchide.
`Tor
`examgdie, LIPFe. LIBF,. SbF, LIAGFs, EISQs0Fs, LIN(SOd0F so, LIN(SQCaF5h,
`
`UIN(SO,CF«NS O00Fa) and LCOS a}, Tha ithiuem sat car be one ifttunysall selected from these and usedalone.
`Affematively, the ithiurn sal Gan be a mixture of hwo of more Hthium salts selected Fram hese. The corcerntration of the
`HintSatis im ie rare of for example, 0.5 fa oS omoaviter.
`{G700}. A.gel electrolyte can be a palymer matedal soaked with a. nenaquecus liquid electrolyte. The paiymer mataral
`may be, forexampie, palyeihylene axide, palyecrianiie, palywinylidene Ruaride, nalymethy! methacviate, or a polymer
`having ethylene oxacde bonds.
`[OiGTy As a component ofan tonic liquid, a cation may be, for example: a.quatemary salt having aliphatic chains, such
`as a leveatkyiamimnonium or ietaaikyichasphoniunm, an ammonium haviag en aliphatic ring, such as a pyrohdiniten,
`Torphotniam imidazolium, tetrahydrapyndiniongiperazinium, oF piperidiniun, or a nllvoder-containing heterocyclic
`aromatic cation, such as a pyndinium of imidazolium. As aconpanen! of arionic injuid, an anion.may be, for exameale,
`PFgoBg, SbFg- ASFg SOQCFsy, MiSOoCFsie, MISOoCoFsty NISQOUFgHSOCyFay, or COSOQCEg}aAn ionic gid
`may conlanra lithium sail.
`{G702}. Al least one of the postive electrode 201, eleciraiyle layer 802, and negative elactrade 203 may cantain 38
`binder for improved adhestun behween paricies. The binderis used to improve the binding together of the materials
`farming the stectradeis). Examines of binders inciude maternais sucthas polyyvinyintene fluoride, pulyletrafrorceityieane,
`polyetiviens, polorapvlens, aramid resins pohyamides cokimides, palyamide-imicdes, polacndaniiiie, solyaoryic ankt,
`methyt polyacrylate ester, ethy! pohvatrylate ester, hexpolyacrylate ester, palyrmethacnhe acid, raeihyl poyymethacr-
`yiete easter, ethy? palymeiiseniate aster, hexyl patymethacryiate ester, pobvinyl aceiate, poh winylpyrrofcdane,. paty-
`eihers, palyethersuliones, hexatnuoripolypropyviene, shyrens-butadiene rubber, and carboxyrethy! cellulose. A binder,
`furthermore, can be a coapalymerof two or niore matenals selected frorm the group consisting of telrafkiorgethylene,
`hevatiuaroethyiene, hezafuorapropyiene, pertiuoroalky! vinyl ethers, vinikiens fluoride chiocatrifluaroeihyens, ethy-
`ene propylene, pentaluorgrapyiens, fluaramethy! wind etheracrylic acid, and hexadiene, trneayaise be that a mixiuce
`of two urmore matefisis selected from these is used asa binder,
`
`{8103} Atleast one of the postive electrode 201 and negative slectrade 203 may optionally contaebt a conduciveagent.
`{8194} The conductive agent ia used te reduce: ihe -elacirical resisiance of the elecirodais). Examples of conductive
`agenis inchide maternais such as hoes of araghite, which are natural graphite or artificie! qraphite, carbon packs, such
`as acetylene black and Ketienblack..camduetive Sbhers.such as carton fiber and metallic fiber. cmietalic pawders, for
`example of fuorinated carbon or aiwninum, conductive whiskers, tor exarmygne of zinc oxide or potassium tanate, con-
`ductive metal oxkles, such a5 ianium conte, and conductive palvymers, such as polyamine, palypyrraie, and point
`ophene. The use of a carbun-conductive auenias a conductive agent is & measure for cost reduction.
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`405] Hatteries acourding ie Embodiment 3-can-be configured as butleries.in various shabes, inciting ccin-shaped,
`cylindrical, square, sheei-shaped, tution-shaped, faitpiste,