(12) INTERNATIONAL
`APPLICATION PUBLUSHED UNDER THE PATENT COOPERATION TREATY (PCP)
`(18) World fatellectual Praperty
`A
`Organization
`International Burcass
`
`HTTEEE
`
`{10} Enternational Publication Number
`WO 2017/108108 Al
`
`AG. AT, AU, AZ, BA, BB, 8G, BH, BN, BR, BW, BY,
`
`
`
`
`BA, CA, CEL CL.
`CM,
`OO, OR, OU, 2. DE DR. OM,
`
`
`pO, HS, EC. EB,
`E
`30, GE, GH, GM, GY,
`HN. HB. HL TD, fL, PN, IR, 1S JP, KE, KG, RN. RP. KR,
`KX. LAL LO. LK. LR, LS.
`LoL
`bY. MA, MD. MEL MG,
`SIR, MN, MW, MIS, MY, MZ,
`
`'N
`
`
`
`fo
`inaficated, for euary
`o>
`ARIPO (BW Gu,
`:
`
`
`WL SD, SL. SP, Sz.
`MW, MZ, Ne
`
`}, Burctsian (AM. AY, BY. KO, KF. RU,
`.
`
`, FM, Berepean OAL. AP BE. BGO, CHL CY, C2, DE,
`DK, BE, BS, PT, FR. GB, GR, HR, HU, PR 1S, PR LT. Lu
`LY, MC, ME, MT, NE NQ, FL, PY, RO, RS, SE. Sh SR,
`
`SM PRR DAPI (BR. BE CP, OO, 01, CM, CLA, GN, GO,
`GW RM ML, MR, NE, SS, TR) PG).
`Published:
`
`(84
`
`wih Dversaional search repert cart 22630)
`
`(43) faternational Publication Date
`29 Jaume BY (294.2017)
`
`Wi
`
`infernational Patent Classifivatiwm:
`FROIAT FG°GF25 (QOL) AGL IF (2006.03)
`CONF840 C100607}
`ATGIST FRUSH? CAO
`
`International Appication Nunxber:
`
`PCCTVEPRIO1 S08 11S
`
`interastional Filing Bate:
`
`22 Decertber 2014 (22. P2.208S)
`
`Filing Languages
`
`Publication Laspuage:
`
`Fan
`
`Enetish
` . AY.
`Applicant: TOYOTA MOTOR EEROPE [RE/RE]
`enue do: Goerget 60, 1140 Brussels (BEY.
`
`inventor; KATOR, Waki 46 roe Honrottic, £13) Brussels
`(BE)
`
`Agents! HART-DAVES, dasen ot al; Cabinet
`Lormenic,
`§S8 Roc de Miaiversite, 75340 Paris
`(PR).
`
`Baan Be
`Cydon OF
`
`Designated States (anvess etherwive brdicuted,
`
`ere ovcdtantdes.
`fied of? aeatiena! profes
`AE, AQ, AE
`
`
`
` MATERIALS GOR SOLID BOSCTROLYTE
`
`Exige
`F438 78
`
`Cumparativ: Exampicl
`3. dies}
`
`1408-08
`
`1 OCR OS
`
`
`
`fonicconductivity(2cur} 2.OORfe
`
`BODE
`
`B.008-04
`
`4.00r-a4 §
`
` O.O08+G0
`8
`2.88
`a4
`
`
`
`
`
`
`¥ in (1-YYLEgpooyMS(SX ahd YIPS2g)
`
`Figure 14
`
`(ST) Abstraci: The present invention relates io a material containing the elements li, M. B.S and X wherein M« $1, Ge or Sa. and
`KX SP LCL By ork. Phe aederial cen be used asa suffice solid clecirnivie material, notably fae an all-solid-state Jithhue battery.
`
`ssALMEPane?
`
`Nao
`
`WO2017/1°
`
`

`

`WO 2097/ 1U8 10S
`
`BOTAEP2H S/O8 1099
`
`Materials for solid electrolyte
`
`Field of the invention
`
`The present invention relates to a material containing the elements Ui, M,
`P, S and X wherein M = Si, Ge or Sn, and X = F, Ci, Br or 1. The material can be
`
`used as a sulfide solid electrolyte material, notably for an all-solid-state fthium
`
`battery.
`
`Backoroundart
`
`
`
`
`10
`
`The solidfication of the electrolyte provides an advantage for use in
`
`battery applications.
`
`In the case of the all-solid-battery system,
`
`the non-lquid
`
`nafure of the electrolyte allows stacking of the battery cells in a single package
`
`without an ionic short circu. Such a battery configuration decreases the dead-
`
`space between the single cells.
`
`In addition,
`
`this
`
`structure
`
`is suitable for
`
`15
`
`applications requiring a high voliage and limited space, such as vehicle power
`
`sources.
`
`In the
`
`basic structure
`
`of an exemplary all-solid-state
`
`battery the
`
`folowing layers are arranged in order: cathode current collector, cathode, satid
`
`siectrolyte, anode, anode current collector. Further layers may be present - for
`
`20
`
`example, a buffer layer may aiso be interposed at the cathode/solid electrolyte
`
`interface in order to enhance lithlum-ion transfer at the interface.
`
`As representative examples of known cathode active materials for ithiurn
`
`all-solid-state
`
`batteries, LiCoD, and LiFePO, may be cited. The negative
`
`electrode active material may be, for example, a carbon active material or a
`
`25
`
`metalalloy-based active material.
`
`Concerning the solid-state électrolyte, a certain number of oxide-based
`
`or sulfide-based materials are known. Oxide-based solid electrolyte materials
`
`for Hthium all-salid-state batteries typically contain Li and O, and offen also a
`
`fransition metal and/or metal/metalicid from group 13/14 of the Periadic Table
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`fe.g.
`
`AL Si, Ge}, and/or
`
`phosphorus. Known materials
`
`in this context
`
`include
`
`UPON (or
`
`example,
`
`U29P03.5N0.46),
`
`LiLaTiO {for
`
`example,
`
`LioS4La,-5SITIQ5),
`
`LilazrO (fer example, Li,La,Zr,Di2). Compounds which have a NASICON mold
`
`structure
`
`can also be mentioned
`
`e.g.
`
`the compound denoted by general
`
`formula
`
`Lif+xAl Ge,-x(PO4)3 (0 & xX S 2} or the compound
`
`denoted
`
`by general
`
`formula
`
`Lif+xAixTi2-x(PO,33 (0 sx S 2. Another possibility is a lithium borosilicate.
`
`Gonceming
`
`sulfide-based
`
`electrolyie materials,
`
`known materials
`
`include
`
`ones containing
`
`Li, S, and possibly one or more of P, SiGe (also group
`
`13
`
`Lil ,GeP2Si2,
`for example,
`In}. Known possibilities melude,
`B, Al, Ga,
`elements
`U2S-P285 and U26-P2S5-Ul, Li2S-P,ssiiz0,
`LAS*SsI4O-Lil,
`——Li,8-SIS, and Lis
`SiS2-Li, Li,S-SIS,-LIBr, LI,S-SIS,-LIC!, Li2S-SiS2-B283 -LH, LigS-SIS,-P2s,-Lil, Li,S-
`
`B28, Li,5-P2S5-2_.5. (m and n being positive numbers, 2 being Ge, Zn, or Ga},
`
`Li,5-GeS, and Li,S-SiS,-Li,PQ 4. and Li,S-5iS2-Li,MOy (where x and y are positive
`
`numbers, M is P, Si, Ge, B, alurninum, Ga, or In etc.) The description
`
`of the
`
`use the
`solid electrolyte materials which
`refere to sulfide
`“U2S-P285“
`above
`compasition
`containing Li,S and P2s6 in varying
`relative amounts,
`the
`material
`same naming convention
`referring to other descriptions hereinabove.
`
`with
`an
`WO eniaoages4
`discloses
`a sulfide-based
`solid
`electrolyte
`there is a
`argyrodite
`type crystal {Li,_,Si,Pi-x86}. However,
`here it appears that
`problem af low janic conductivity
`due tothe high PF content
`- without wishing to
`
`be bound by any particular
`
`theory,
`
`i is believed that
`
`the interaction
`
`of PS,° and
`
`Lit decreases ionic conductivity.
`
`10
`
`i5
`
`20
`
`Similarly,
`
`in Rao Rayavarapu
`
`et al. J. Solid State Electrochem.
`
`(2012)
`
`16 5 1807-1843,
`
`the authors
`
`investigated
`
`an argyrocdite
`
`type
`
`crystal with
`
`the
`
`25
`
`composition
`
`of
`
`tiepssx (X=Ci.Brj,
`
`and aiso in Boulineau
`
`et al. Solid’ State
`
`lonics 221
`
`(2012)
`
`1-8.
`
`the authors
`
`investigated
`
`an argyrodite
`
`type crystal with
`
`the composition
`
`of Li,PS.x (X=Cl,BrJ}
`
`In these cases,
`
`it
`
`is considered
`
`that
`
`a
`
`probieni of low ionic conductivity
`
`arises for the same reasons as given above.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`Summary of the invention
`
`The present
`
`invention has been carried out with a view fo solving
`
`existing problems in the field of solid electrolyte materials for use in all-solid-
`
`in particular with a view to providing materials with high fonic
`battery systems,
`conductivity,
`and consequently higher output
`for a batfery,
`in particular a
`
`lithium battery, containing such solid electrolyie materials.
`
`in one aspect, the present invention relates to a material comprising the
`
`eaferents LIM, P. Sand X,
`
`id
`
`wherein M is at least one element selected from the group consisting of
`
`5i, Ge, and Sri and
`
`X is at least one element selected from the group consisting of F, Ci, Br
`
`and |.
`
`.
`
`in another aspect,
`
`the present
`
`invention
`
`relates fo a process for
`
`is
`
`preparing a material according to the invention comprising the elements Li, M,
`
`P Sand X, the process comprising the steps of
`(a) providing the solid sulfides Li,8, MS, (M = Si, Ge or Sn) and P,S,, as
`well as LiX (X = F, Ci, Br, 1) as dry powders,
`in the stoichiometric proportions
`
`corresponding to the target product, and mixing the powders;
`
`20
`
`(b} milling the modure obtained in step (a} under an inert atrnosphere:
`
`(c} heating the milled mixture obtained In step (b) at a temperature T of
`
`300°C < T < 700°C, under a pressure FP of 0.1 Pa < FP < 200 Pa, for @ duration
`
`tof ih sts 50h.
`
`in another aspect,
`
`the present
`
`invenfion relates to an all-solid-state
`
`29
`
`lithium batlery comprising the following elements:
`
`- a poshive electrode active material layer:
`
`-asolid electrolyte:
`
`- a negative electrode active material layer,
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`wherein the solid electrolyte cantains a material of the invention comprising the
`
`elements Li, M. PB S and x.
`
`Brief description of the drawings
`
`Figure 1 shows the ionic conductivity of sulfide solid electralyie materials
`
`prepared in the Examples and Comparative Example.
`
`Figure 2 shows a-ray diffraction (XRD} measurements of sulfide solid
`
`electrolyte materials prepared in the Examples and Comparalive Example.
`
`10
`
`Detaled description of the invention
`
`The present
`
`invention relates, most generally,
`
`to a material corwmrising
`
`the elemenis UM, P, S and X,
`
`15
`
`wherein Mis at least one element selected from the group consisting of:
`
`Si, Ge, and Sn: and
`
`X is at least one element selected from the group consisting of F, ci, Br
`
`and [.
`
`Such a@ material comprising the elements Li, M, P, S and xX, can for
`example, be prepared from:
`Li precursors including Hthium in the elemental
`
`20
`
`state as well as lithium halides Lix (X being as defined above), M precursors (Le.
`
`Si, Ge or Sn precursors) including M (.e. Si, Ge or Sn) in the elemental state or
`
`as sulfides such as SiS, sulfur. (S)} precursors inctuding elemental
`
`sulfur or
`
`sulfides including LipS, MS, (e.g. SIS.) and phosphorus sulfides such as PSs,
`
`25
`
`and phosphorus (P} precursors including elemental phosphorus, phosphorus
`
`sulfides such as P,Ss and phosphorus halides such as PBrs.
`In an exemplary method of preparing 2 material comprising the elements
`U, M, PS and & according to the invention, a melt quenching method can be
`
`applied as well as a ball miling proceclure. Thus,
`
`in a typical synthesis mathaod,
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`ball milling is used to thoroughly mix solid precursors in a powdery state. Apart
`
`fromm ball milling, vibration milling and jet milling are also passible techniques.
`
`After the mixing of starting materials in the appropriate molar ratio,
`
`they may
`
`be put info a glass tube,
`
`the glass tube sealed under vacuum, and the sample
`
`heated at a high temperature,
`
`typically over BOO°C,
`
`in order to melt the starting
`
`materiais,
`
`this temperature being kept for 8h. Then the glass tube may be put
`
`into ice water for quenching.
`
`in one advantageous method according to the invention,
`
`using some
`
`appropriate
`
`precursors,
`
`the
`
`invention
`
`includes a process for preparing a
`
`10
`
`material according to the Invention,
`
`the process comprising the steps of:
`
`{a) providing the solid sulfides 11,8, MS, (M = Si, Ga or Sn} and PSs, as
`
`well as LIX (X = FB Cl. Br, f) as dry powders,
`
`in the stoichiometric proportions
`
`corresponding to the targef pracduct, and mixing the powders:
`
`ib) milling the mixture obtained in step (a} under an inert atmosphere:
`ic) heating the milled mixture obtained in step {b} at a temperature T of
`300°C s T s 700°C, and preferably 450°C 2 T = 550°C, under a pressure P of
`0.1 Pas Ps 200 Pa, and preferably [Pa < Ps lOOPa, for a duration t of [h <
`
`t <= 50h, and preferably Shs t < iOh.
`the milled mixture. obtained in step is
`In step (c),
`the heating of
`preferably carried out at a temperature T of 450°C < T < 550°C, under a
`
`i5
`
`20
`
`pressure Poaf |IPa < Ps iOOPa, and/or for a duration t of 3h < ft <=
`iGh.
`The milling step (b) is of importance, notably for increasing the melting
`
`temperature
`
`of starting materials by generating Li,PS,. As
`
`regards milling
`
`techniques, apart from ball milling, vibration milling and jef milling are also
`
`25
`
`possible. The inert gas in siep (b} may be, for example, nitrogen or argon and
`
`is preferably argon.
`
`in materiais according to the invention comprising the elements Li, M, P,
`
`S and xX, wherein M is Si, Ge and/or Sn, and X is F, Cl, Br and/or
`
`f,
`
`in
`
`advantageous
`
`embodiments,
`
`M is Si Also,
`
`in
`
`further
`
`advantageous
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`embodiments, X is Br. In preferred materials according to the invention, M is Si
`
`and Xis Br.
`
`Preferred materials
`
`according to the
`
`invention
`
`have a composition
`
`represented by the following general formula (1):
`
`(I-Y)[Li4 , (26pems¢ (Si -9x ,)x]-¥(PS2.5)
`
`(4)
`
`wherein
`
`05s xs 2;
`
`O< 8s 1: and
`
`19
`
`@< ¥ < 0.5.
`
`As mentioned above,
`
`in advantageous embodiments, M is Si and/or X is
`
`Br,
`
`Advantageously,
`
`in materials represented by general formula (1} above,
`
`45
`
`xis O=.7 =< x < 1.5, preferably 0.8 < x < 1.3, more preferably 0.9 < x s 4.4, and
`
`most preferably x is substantially equal to 1.0.
`
`Furthermore, advaniageously 0.3 s 6 <= 0.7, preferably 0.4 < 8 < 6.6,
`and most preferably 6 is substantially equal to 0.5.
`
`Furthermore, advantageously 0.05 < Y < 0.35, and preferably 0.70 < ¥
`
`20
`
`= 0.25.
`
`it
`
`is considered that the preferred ranges for ¥, x and & are substantially
`
`independent of
`
`the choice of M and xX, on account of crystal
`
`structure
`
`constrainis.
`
`[tf may be considered that preferred materials according to the
`
`invention and represented by general formula (1) above have a basic structure
`
`25
`
`determined essentially by that of U4mMS4. for example LigSiS, for M = Si. When
`
`part of the sulfur (S$) is replaced by halogen. (4) and extra passis added, a new
`
`phase can be obtained. Since this material
`
`is crystalline and mostly consists of
`
`MS, (e.g. SiS,} tetrahedra of the mother composition,
`
`this constrains the effect
`
`of additional X and P and available sites.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`Preferred materiais according to the
`
`invention
`
`show,
`
`In an X-ray
`
`diffraction measurement using @ Cua fine, a peak in the positions of
`29=16.26°
`{+ 0.50°), 17.4° (+ 0.50"), 25.06° (+ 0.50°), 29.48°
`(+ 0.50°),
`and 30.08° (+ 0.50°}),
`
`in a further aspect,
`
`the present
`
`invention relates to an all-solid-state
`
`fthium battery comprising the following elements:
`
`- a positive electrade active material layer;
`
`~ a solid electrolyte:
`
`~ a negative electrode active material
`
`layer,
`
`10
`
`wherein the solid layer contains a sulfide-type material accerding to the present
`
`invention, containing slements Li, M, P, Sand X, as defined hereinabove.
`
`in such an all-solid-state
`
`(ithium battery according to the present
`
`invention, using as solid electrolyte,
`
`the solid sulfide materials of the invention,
`
`concerning the form of
`
`the solid electrolyte materials, examples include a
`
`is
`
`particle shape, such as the shape of a true ball and the shape of an elliptical
`ball, or a thin film form,
`for example. When solid electrolyte materials have a
`particle shape, as for the mean particle diameter, 8 is preferable that their size
`
`is within the range of 50 nm to 10 micrometers, more preferably within the
`
`range of 100 nm to 5 micrometers.
`
`20
`
`Atthough i is preferable to have only one or more solid electrolyte
`
`this layer may also
`materials as mentioned above in a solid electrolyte layer,
`contain a binding agent
`if needed. As a binding agent used for a solid
`
`eiectrohie layer,
`
`this may be of the same type as mentioned herein for the
`
`positive active material
`
`layer.
`
`25
`
`As regards the thickness of a solid electrolyte layer, although this may
`
`change with the kind of solid electralyie materials, and the overall composition
`of an ail-solid battery, ‘generally ii
`is preferable that this thickness is within the
`range of 0.1 micrometer to 1000 micrometers, more preferably within the range
`
`of O.4 micrometer to 300 micrometers.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`Cenceming the positive acive material
`
`(cathade active material) used for
`
`the present
`
`invention, which can be used in the pasiive electrode
`
`{cathode}
`
`active material
`
`layer,
`
`this
`
`is not especially Hmted
`
`9 the average operating
`
`potential becomes more than 4 V (vs. LULI*). As an average operating potential
`
`of positive active material,
`
`this is appropriately more than 4 V {vs. LI/Li*}, and it
`
`is preferable that
`
`# is within the limite of 4.0 Voto 6.0 V, stil more preferably
`
`within
`
`the limits of 4.5 V to 5.5 V. The average operating
`
`potential
`
`in the
`
`present
`
`invention can be evaluated using cyclo voltammetry,
`
`for example.
`
`In
`
`particular, when cyclic voltammeiry
`
`is measured at a small electric potential
`
`10
`
`speed like 0.1 mV/sec,
`
`it can be considered that
`
`the average value of the
`
`vollage which gives the peak current on the side of oxidation,
`
`and the voltage
`
`which gives the peak current on the side of reduction is the average operating
`
`potential.
`
`AS @ positive active material, especially if ihe average operating potential
`
`15
`
`is made with more than 4 V ivs. Li/Li*}, there is no specific limitation,
`
`but i js
`
`preferable that
`
`the material
`
`is an oxide positive active material, which can have
`
`a high energy density.
`
`A compound which has the spinel
`
`type structure
`
`denoted by general
`
`formula LIM,0,
`
`(Ml
`
`is at
`
`least one kind of transition metal element),
`
`as an
`
`20
`
`example
`
`of positive
`
`active material,
`
`can be mentioned
`
`as an example. As
`
`regards M of the above-mentioned
`
`general
`
`formula
`
`LIVM,O4, especially if
`
`if
`
`is a
`
`transition metal element,
`
`it will not be limited, but
`
`it
`
`is preferable that
`
`it
`
`is at
`
`least one kind chosen from the group which consists of Ni, Mn, Cr, Co, V, and
`
`Ti,
`
`for example, and # is more preferable that
`
`# ie at
`
`feast one kind chosen
`
`25
`
`from the group which
`
`consists of Ni, Mn, and Cr especially.
`
`Specifically,
`
`LiGre, QSNic.50Mn14504,
`
`LiCGrMnd », LiNio.SMn1.504, etc.
`
`can be mentioned. The
`
`compound which has the olivine type structure denoted by general
`
`formula
`
`LIMPO , (Mis at Jeast one kind of transition metal element} as other examples of
`
`positive active material can be mentioned. M in the above-mentioned
`
`general
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`formula will not be limited especialy if it
`
`is a transition metal element, but # is
`
`preferable that
`
`it.
`
`is at
`
`least one kind chosen from Mn, Co, Ni, and the group
`
`that consists of V, for example, and it
`
`is more preferable that
`
`it
`
`is at feast one
`
`kind chosen from the group which
`
`consists of Mn, Co, and Ni especially.
`
`Specifically, LIMNFO,, LiICoPO4, LINIPO,, etc. can be mentioned, The cornpound
`
`which has the layer structure denoted by general formula LIMO, (M is at least
`
`4
`
`type of a transition metal element) as other examples of positive active maternal
`
`oan be mentioned. Specifically, LICoO,, LINggMny.s8@, and LINio.33Co0.33Mno.33C7
`
`aic. can be mentioned. As examples other
`
`than the posHive active material
`
`10
`
`mentioned
`
`above,
`
`a LipMn0 .-LINN),Col/.Mni/30,
`
`solid
`
`solution,
`
`a Li,Mnd.-
`
`LINIo.SMint.S5Cb
`
`solid solution,
`
`a Li,Mnd ,LiFeQ.,
`
`solid
`
`solution,
`
`etc.
`
`can be
`
`mentioned.
`
`As regards the form of the positive active material, a particle shape, such
`
`as the shape of 4 true ball and the shape of an elliptical ball, thin film form, etc.
`
`15
`
`can be mentioned, as an example. As for the mean particle diameter, when the
`
`positive active maternal has a particle shape,
`
`it
`
`is preferable that
`
`it
`
`is within the
`
`size range of 0.1 micrometer
`
`to 50 micrometers,
`
`fer example. As for
`
`the
`
`content of the positive active material
`
`in @ positive active material
`
`layer, i is
`
`preferable
`
`that
`
`#t
`
`is in the range of 10 % by weight
`
`to 99% by weight,
`
`for
`
`20
`
`example, more preferably from 20 % by weight
`Goneerning the positive active material
`
`fo 90% by weight.
`layer,
`in addition to the positive
`
`active material mentioned above, # needed.
`
`the positive active material
`
`layer in
`
`the present
`
`invention may contain other materials,
`
`for example, solid electrolyte
`
`materiais etc. As for the content of the solid electrolyte materials
`
`in a positive
`
`25
`
`active material
`
`layer, # is preferable that this content
`
`is 1% by weight
`
`to 90%
`
`by weight, more preferably 16 % by weight
`
`to 80% by weight.
`
`Furthermore,
`
`a positive active material
`
`layer may contain an electrically
`
`conductive agent
`
`from a viewpoint
`
`of improving the conductivity of a positive
`
`active material
`
`fayer, other
`
`than the solid electrolyte materials mentioned
`
`

`

`Wilh 209 7/0815
`
`‘
`
`POCTEPIOUS/O8 1019
`
`10
`
`above. As electrically conductive material.
`
`acetylene black, Ketlenblack, a
`
`carbon fiber, etc. can be mentioned,
`
`for example. A pasitive active material
`
`may also contain a binding agent. As such a binding material
`
`(binding agent),
`
`fluorine-based binding materials,
`
`such as polyvinylidene fluoride (PVDF) and
`
`polytetrafiuorcethylene
`(PTFE), efc. can be mentioned, for example.
`Although the thickness of a positive active material
`layer may change
`
`according to the kind of all-solid-state battery made,
`
`it
`
`is generally preferable
`
`that # is within the range of G.1 micrameter ta 1000 micrometers.
`
`As
`
`regards
`
`the
`
`negative
`
`electrode
`
`active
`
`material
`
`layer
`
`10
`
`in the present
`
`invention,
`
`this
`
`layer at
`
`least contains one or more negative
`
`electrode active material{(s}, and may additionally contain at least one or more
`
`of solid electrolyte materiais and electrically conductive agents if needed. For
`
`all-solid-state Hthiurnm batteries,
`
`the negative electrode active material
`
`is not
`
`limited
`
`provided thaf occlusion and discharge of
`
`the
`
`Li
`
`ion, which is a
`
`iS
`
`conduction ion, are possible. As a negative electrode active material, a carbon
`
`active material, a metal active material, etc. can be mentioned, far example. As
`
`@ carbon active material, black lead, meso carbon micro beads (MCMB), highly
`
`ordered / oriented pyrolytic graphite (HOPG), hard carbon, sof carbon, etc. can
`
`be mentioned as examples. On the other hand, as a metal active material,
`
`20
`
`charges of an alloy, such as Li alloy and Sn-Co-C,
`
`In, Al, Si, Sn, atc. can be
`
`such as LiTi,Ql,, can be
`mentioned as examples. Oxide stock materials,
`mentioned as examples of other negative electrode active materials.
`
`Conceming solid electrolyte materials used for
`
`the negative electrode
`
`active material
`
`layer, and an siectricaly conductive agent,
`
`these may be the
`
`25
`
`same as that for the solid electrolyte layer and positive active material
`
`layer
`
`mentioned above.
`
`The thickness
`
`of
`
`the negative
`
`elecirode
`
`active material
`
`layer will
`
`generally be appropriately within
`
`the range of 0.1 micrometer
`
`to 1000
`
`micrometers.
`
`

`

`WO 2A E71 88208
`
`PCT/EP2OTSAISTOLS
`
`21
`
`An all-solid-state battery of the present invention Ras al least the positive
`
`active material
`
`layer,
`
`solid electrolyte
`
`layer. and negative electrode
`
`active
`
`material
`
`layer which were mentioned above.
`
`{f further usually has a positive
`
`pole collector which collects a positive active material
`
`layer, and a negative pole
`
`collector which performs
`
`current
`
`collection
`
`of a negative electrode
`
`active
`
`material
`
`layer. As a material of a positive pole collector,
`
`for exarnple, SUS
`
`istainless
`
`steel},
`
`aluminum,
`
`nickel,
`
`iron,
`
`fitlantum,
`
`carbon,
`
`etc.
`
`can
`
`he
`
`mentioned, and SUS is especially preferable. On the other hand as a material of
`a negative pole collector, SUS, copper, nickel, carbon, etc. can be mertioned,
`far example, and SUS is especially preferable. Concerning the thickness,
`form,
`
`10
`
`etc, of a positive pole collector and a negative pole collector,
`
`the person skilled
`
`in the art may choose suitably according to the use of
`
`the all-solid-state
`
`battery, etc. The cell case used for a common ail-solid-state baftery can be
`used as the cell case used for the present
`inverfion,
`for example,
`the cell case
`
`15
`
`made from SUS, etc. can be mentioned. The all-solid-state
`
`batiery of
`
`the
`
`present
`
`invention may form a power generation element
`
`in the inside of an
`
`insulating ring.
`
`The all-solid-state baftery of the present
`
`invention can be considered as
`
`a chargeable and dischargeable ail-sclid-state battery in a roam temperature
`
`20
`
`environment. Alfhough i may be a primary battery and may be a rechargeable
`
`battery as an all-solid-stafe battery of the present
`
`invention,
`
`& is especially
`
`preferable that
`
`it
`
`is a rechargeable battery. Concerning the form of the all-solid-
`
`state batiery, a coin type, a laminated type, cylindrical, a square shape, etc.
`can be mentioned, as examples.
`.
`
`25
`
`As regards the manufacturing method of the all-solid-state battery of
`
`the
`
`present
`
`invention,
`
`this
`
`is
`
`not
`
`particularly
`
`limited,
`
`and
`
`cammon
`
`manufacturing methods of all-solid-state batteries can be used. For example,
`
`when an aill-solid-state battery is in the thin film form, a positive active material
`
`layer can be forned on a substrate,
`
`and the method of
`
`forming
`
`a solid
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`iz
`
`electrolyte layer and a negative electrode active material
`
`layer in order, and
`
`laminating them thereafter etc., may be used.
`
`Within the practice of the present
`
`invention,
`
`it may be envisaged to
`
`combine any features or embodiments which have hereinabove been separately
`
`set out and indicated to be advantageous, preferable, appropriate or otherwise
`
`generally applicable in the practice of the invention. The present description
`
`should
`
`be considered to include
`
`all
`
`such combinations
`
`of
`
`features
`
`or
`
`embodiments described herein unless such combinations are said herein to be
`
`10
`
`mutually exclusive or are clearly understood in context fo be mutually exclusive.
`
`Experimental section - Examples
`
`The following experimental section itustrates axperimentally the practice
`
`of the present invention, but the scape of the invention is not to be considered
`
`1s
`
`to be limited to the specific examples that follow.
`
`The
`
`solid
`
`electrofyies
`
`of
`
`G-Y}ILI 4, @s).«ms, isi sxSix]-¥ (es,.5 were
`
`synthesized and their conductivity was tested, wherein M=Si, X=Br, x=l
`
`and
`
`S<0.5 for the following Examples.
`
`20
`
`Synthesis of solid electrolytes
`
`Example 2
`
`The solid electrolyte of o.35(Li, 4818, 58ra5)-0.15(Ps,,)
`
`[Y=0.15] was
`
`25
`
`synthesized using starting materials Li,S (Nihon Chemical Industry), SiS, (Alfa
`
`Aesar), LIBr (Kojundo Chemical Lab.) and r,s, {Aldrich}. They were mixed at
`
`the weight ratio Gisted in Table 1) and put into the zirconium pot cas mL} with
`
`210 Zirconium balis @ 190 mm) under argon. The pot was closed and treated with
`
`planetary milling equipment
`
`(Fritsch, ev; at 370 rpm for 46 h to obtain the
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`33
`
`precursor, The precursor was sealed inio the glass tube af the pressure of 30
`
`Pg and then hegted af 500°C for 8 bh.
`
`Examples 2 to 4-and. Comparative Examnle 1
`
`
`
`
`The same procedures were performed as given above in Example 4
`
`except for the weight
`
`ratio of starting materials listed hereunder as Table 1.
`
`Table 1: Weight ratio of starting materials
`
`
`
`
`
`
`
`Measurement of Li ion conductance
`
`Li
`
`jon conductance at a temperature of 25°C was measured while using
`
`i5
`
`the
`
`sulfide
`
`solid
`
`electrolyie material
`
`obtained
`
`in Examples
`
`t
`
`to 4 and
`
`Comparative Example 1. First, 100 mq of the sulfiie solid electrolyte material
`was added to a cylinder made of macole and pressed at 4 tan/om 2 to form a
`
`olid eleciralyie layer. The pellet was sandwiched by SUS current collector for
`
`measuring impedance spectroscopy.
`
`20
`
`An impedance gain-phase analyzer manufactured by Siolegic (/MP3} was
`
`used for
`
`the measurement
`
`as FRA {Frequency Response Analyzer). The
`
`measurement was started fram a high-frequency range usinge conditions of an
`
`alternating vollage of 5 mV, a frequency range of
`
`1 Hz to 1 MHz. The ionic
`
`conductivity of each of the materiais are shown in Fig. 1.
`
`25
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`44
`
`X-Ray Diffraction Measurement.
`
`X-ray diffraction measurernent
`
`(using a Cuka line} was performed by
`
`using the sulfide solid electrolyte materials obiained in Examples 1 fo 4 and the
`
`comparative
`
`samples obtained in Comparative Example 1. The results are
`
`shown in Fig. 2.
`
`A peak in positions of 29=15.26°
`
`(+ 0.50°), 17.4° (+ 0.50°), 25.06° (+
`
`0.50°},
`
`29.48"
`
`(+ 0.50°),
`
`and 30.08°
`
`{+ 0.50°)
`
`In an X-ray diffraction
`
`measurement using a Cuka line was observed for Examples tio 4. in the case
`
`19
`
`of Comparative Example 1, the target crystal was not obtained.
`
`The X-ray diffraction measurement was carried out under the following
`
`measuring conditions:
`
`—
`
`« Wavelength of X-ray : 1.54184 (Cuika line)
`» Tamperature : 29°C
`
`15
`
`« Machine >: Rigaku Uliima Hl
`
`- Detector : D/teX URra
`
`« Step : 0.07"
`
`“1S. 3
`
`© RSP > 8 mm
`
`20
`
`* RS2 2 13 mm
`
`* Tube voltage © 45 kV-
`
`- Tube current «200 mA
`
`It
`
`is considered that as long as the CukKa beam is used, the same Bragg
`
`peaks will be observed even if exact machine and measuring conditions are
`
`as
`
`varied.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`a5
`
`Claims
`
`1.
`
`A material comprising the elements Li, M, P. S and x,
`
`wherein M is at least one element selected from the group consisting of:
`
`Si, Ge, and Sn: and
`
`X is af least one halagen element selected frorn the group cansisting af F,
`
`cL Brand |.
`
`10
`
`2.
`
`A material according to claim 1, wherein the material has a composition
`
`represented by the following general formula (1):
`
`CY)LE 4. 2-5)kMS,(S, 5K px Y(PS2.5}
`
`(1)
`
`wherein
`
`is
`
`O5 ax2;
`
`Qs8< 1; and
`0 «< y = 0.8.
`
`20
`
`3.
`
`4.
`
`A material according to claim 1 or.2,.wherein M is 8b
`
`A material according to any of claims 1 to 3, wherein xX is Br.
`
`5.
`
`A material according to any of claims 7 to 4, wherein x is O07 <x = 15,
`
`preferably 0.8 < x = 1.3, more preferably 0.9 < x = 1.1, and most preferably x
`
`25
`
`is substantially equal to 7.0.
`
`&.
`
`A material according fo any of claims 1 fo 5, wherein OS = 8 s O7,
`
`preferably O44 < 6 s 0.6, and most preferably 6 is substantially equal to 0.5.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`16
`
`7.
`
`A material according to any of claims 1 to 6, wherein 0.05 < ¥ 4.0.35,
`
`and preferably 6.10 < Y = 0.25.
`
`in an X-ray
`to 7, wherein,
`17
`A material according to any of claims
`&.
`diffraction measurement using a Cuka Hne,
`the material shows a peak in the
`
`positions of 26 15.26° (+ 0.50"), 17.4° (4 0.50°), 25.06" (4 0.50°), 29.48°
`
`{+ $.50°}, and 30.08" (+ 6.50%).
`
`9.
`
`Process for preparing a material according fo any of claims
`
`7 fo &,
`
`10
`
`comprising the steps of:
`
`{a) providing the solid sulfides Li,8, MS. (M = Si, Ge or Sn) and P.S,, as
`well as Lix (X = F,. ci, Br, 1} as dry powders,
`in the sfoichiometric proportions
`
`corresponding to the target product, and mbing the powders;
`{b} milling the mixture obtained in step {a) under an inert atmosphere:
`(c} heating the milled mixture obtained in step (b)} at a temperature T of
`300°C < T < 700°C, under a pressure P of 0.1 Pa < P< 200 Pa, for a duration
`
`15
`
`tof ih st s 50h.
`
`40.
`
`20
`
`An all-salid-state lithturn battery comprising the following elements:
`~a positive electrode active material layer:
`|
`~a solid electrolyte:
`
`~ a negative electrode active material
`
`layer,
`
`wherein the solid electrolyte contains a material as defined in any of claims 1 to
`
`8.
`
`

`

`Wilh 209 7/0815
`
`POCTEPIOUS/O8 1019
`
`1/2
`
`4406-03 |
`PE
`ye
`|
`
`v2zeoa §|XSBr *
`x=
`SOS
`
`1O0EO3 |
`8.00E-04 |
`Comparative Examplet
`6.00F4 f
`ue Speedos
`
`4.Q0E-O4 §
`
`oo.
`Exempted
`2.56194
`
`conductivity1Scm-4) 200E-O4 § OL CHGE #030 Cpt
`fonie
`
`cenooonnsosnnnesnnoonnnsonnnooonsosnnaocneneensconeosecncee
`0.05
`4
`
`‘
`G45
`
`0
`
`a2
`
`G25
`
`0.3
`
`Yin CA-YHRLaeanlS4(S artyhd Y( PS:5}
`
`Figure 1
`
`

`

`WO 2617108 265
`
`POTEPI01 508 1619
`
`2/2
`
` Example 3
`
`
`
`Example 4
`
`
`Comparative Example 7
`
`peaneeeeneTTTEOE
`16
`20
`26
`36
`38
`40
`
`Figure 2
`
`

`

`INTERNATIONAL SEARCH REPORT international applicationNa
`PCT/EP2015/081019
`
`
`OF BUBSEIY MATHER
`A GLASEAR SATIN
`INYS
`-HOIM10/0525
`GOTD15/00
`ADD,
`
`HOB TO
`
`HOIM1O/0562
`
`Acaeing ic intemationat Pete Ohssticsidn
`8. FEELDS
`SEARCHED
`searched
`Mirkin akuauicmen theater:
`HOM COD HOTS
`
`
` foluseifikartinn
`
`OFC? orig kath material cassiicate:
`
`and UG
`
` ayatuat
`
`falesved by claaviicaken
`
` ayaats}
`
`Rucumedation
`
`searched
`
`ofher
`
`then minivacn documematias
`
`to ise extent
`
`that such documents
`
`are wichuted
`
`is the fletds
`
`
`
`
`
`agateoousing the oferaational gears frac of data tase tere gractcaths,
`
`
`
`. CHEM ABS Data, wp Date
`
`TO SE RELEVANT
`
`Chation of dummamt, with iidicatlon where anurontishe,
`
`af thea rehtaath passage
`
`Retawant
`
`to chet Skt
`
`(UCHIYAMA TAKAYUKI
`us 2094/178768 Al
`eT AL) 26 June 2014 (2014-08-26)
`paragraphs
`[fO0S55}
`,
`[0059]
`
`{oP}
`
`us 200S/O87751 Al CONDO SHIGEO [IP]
`AL) 2 Apri
`} 2009 (2009-04-02)
`tabl e 4
`
`er
`
`(SAMSUNG DISPLAY DEVICES
`oF 198 25 807 AL
`co LTD [KR]) 24 December 1998 (1998-12-24)
`examples 2,.3,5,6
`
`
`
` Fusther thocumenis
`
`contain of Box ©.
`
`att
`
`farpily dines.
`
`* Soetiat ciiageres
`
`af ches documents
`
`3
`t
`
`.
`eo dake Gr priortty
`LG tniieratacad
`ad
`
`* RoeHANt ok
`fe be of par
`
`We Gone stele GFihe ant wien bs not canaidenst
`FRlRORTONe
`
`cro oatem int mubhehed anoraler the iveriaitiinal
`
`ete
`Rak ROE
`sete
`“es
`cannot be
`SEVEN oth clakted irveation
`cessed ch partiontar
`Samisemed
`fo NYMR sete ima
`STE tas GS Oa
`be
`oraiintr
`onluinis?
`oof: griomty
`wey teow doubts
`i iaher atone
`Mee wher
`the document
`
`mahaition, dtr6dsiy oof aricdiae
`
`segaips 2
`orefeeting kiteoral digeiaere
`
`J
`
` athatien ar other ot pe
`Hing diste but fater shart ‘ document member ofthe ss oo
`
`Wacuemne
`
`nee, extibitice
`
`ay other
`
`3 Oktay
`
` farriihy
`