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`1. This document has been translated by computer. So the translation may not reflect
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`(19) [Publication country/region] JP
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`(12) [Kind of official gazette] A
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`{11} [Publication number] 05306117
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`(43) [Date of publication of application] 19931119
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`(54) [Title of the invention] AMORPHOUS LITHIUM ION CONDUCTIVE SOLID ELEC
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`JROLYTE AND ITS SYNTHESIZING METHOD
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`(51) International Patent Classification Sth Edition
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`CGID 15/00 COIBAi?/22
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`COIB 25/30
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`HOIB 1/06
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`HOIM 6/18
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`HOIM 1
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`(21) [Application nurnber] O4114519
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`(22) [Filing date] 199205607
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`(71) [Applicant]
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`{(Name] MATSUSHITA ELECTRIC IND CO LTD
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`(72) [Inventor]
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`[Full name] KONDO SHIGEO
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`[Full name} TAKADA KAZUNORI
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`[Full name} AQTANT NOBORU
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`Overview
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`Chiuse
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`(57) [Overview]
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`PURPOSE: Ta provide a lithium-ion -conductive-solid electrolyte which improves co
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`nventional problems including low chamical stability causing low canductivity or r
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`eduction of conductivity.
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`CONSTITUTION: An amorphaus lithium ion conductive solid electrolyte ali3 PO4 b
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`Li2S.cK.dZ wherein a+b+c+d=1, X is one or more kinds of sulfides selected from
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`SiS2, GeS2, P255 and B2S3, and Z is plural kinds of Hthium halides, is obtd. by m
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`ixing plural kinds of lithium halides with an amorphous compd. expressed by a'Li3
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`PO4.b'Li25.c'X wherein a’+b'+c’=1 and XK is one or more kinds of sulfides selacted
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`from SiS2, GeS2, P255 and B2S3, then heating and melting the mixture, followed
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`by rapid cooling.
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`Patent/Utility Model Document Display | J-PlatPat [IPP]
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`
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`{Patent Claims]
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`[Claim LJ]An amorphous lithium ion conductive solid electrolyte is represented by
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`general formula AIT 3 PO 4. BLi2 S. cx. dZ, wherein a becdis 1, X is one or more
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`sulfides selected frornm the group of SiS? ,GeS? ,P2 S5 ,B2 S3 , and2 is a plurality
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`of kinds of lithium halide.
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`[Claim 2]The amorphous lithium fon conductive solid electralyte accordingto clai
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`m i, wherein the sum of the composition ratios a, 6b, andcisO.9 Zabecs G.4,a
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`nddisQiad 0.6.
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`[Claim 3]A method for synthesizing an amorphous lithiurn ion conductive solid ele
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`ctrolyte according to claim 1 or 2, whereina a’Li3 POd b’ Li 2 G.«c’* X is first us
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`ed. (where a’ b'c" is 1 and ¥ is one or more sulfides selected from the group of
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`SiSZ ,GeS2 ,P2 S55 ,B2 S3 } is synthesized. The method for synthesizing an ameorp
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`hous lithiurn ion conductive solid electrolyte comprises mixing a plurality af kinds
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`of ithium halide Z with an amorphous compound, heating and melting the mixtur
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`e, and then rapidly cooling the mixture.
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` ~~
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`tate at
`say
`Clase
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`{Detailed description of the invention]
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`fooot]
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`lindustrial Application}The present invention relates toa lithium. jon conductive s
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`olid elactrolyte used as an elactrolyte for an electrochemical device such as an all
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`~solid battery, a capacitor, a solid electrolytic display device, ate.
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`f[a002]
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`[Prior art] In recent years, research on development of the lithium secondary batt
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`ery using an organic lithium alectrolyte is done briskly. The active material materi
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`al which was excellent in reversibility as a positive electrode or an anode needsto
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`be developed for development of the lithium secondary battery using an organic e
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`lectrolyte, and such material search is performed briskly today. For example, with
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`respect to a negative electrode material, a Hthium metal alone or a lithium alloy i
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`s used, and @ reaction in which lithium is reversibly taken in between a carbon lay
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`er and a carbon layer is used.
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`(QO03]In addition, as for the positive electrode material, a material in which Li ie
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`ns in an electrolyte go into and out of an active material due to a chemical chang
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`@ caused by an electrochemical oxidation of an active material has been used.
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`fo004]On the other hand, with respect to an electrolyte, a lithium ion conductive
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`solid electrolyte is required to improve the reliability of a battery. However, there
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`is no excellent lithium ion conductive solid electrolyte, and research and develop
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`ment af a new solid electrolyte material has been actively conducted.
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`fOOOS TAs one of studies on such solid electrolytes, Li2 S -& ¢X is one or more sul
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`fides selected from the group of SIS2 ,GeS2 ,P2 55 ,B2 53 } sulfide sulfide glasse
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`s exhibits excellent ion conductivity.
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`Research has been actively conducted,
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`fOOOSILI. sub. 2S. multidet. X (X is one or more sulfides selected from the group
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`of SiS2 ,GeS2 ,P2 SS ,B2 53 } sulfide-based sulfide glasses have particularly high
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`conductivity values in the Li. sub. 2S. Sis. sub. 2 system of the SIs. sub. 2, whic
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`h values are on the order of 5. timas. 10-4. sup. - S fom,
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`{O007]In addition, Li. sub. 2S. multidet. X. sub. 25. multidot. X glass containing
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`lithium iodide added to Li. sub. 2S. multidot. X. mulidot. X sulfide glass is knaw
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`nto have a relatively high lon conductivity of about 10-3 S / cm.
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`[o008]
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`[Problem to be solved by the invention] The conductivity of the Li. sub. 25. mult
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`dot. K OC is ore or more sulfides selected from the group of SiS2 ,GeS2 ,P2 $5 .8
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`253 } sulfide sulfide glasses shows a high valueof 5. times. 10-4. sup. - 5 / cm.
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`sup. 2, as described above, but is still low in ionic conductivity and insufficient in
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`chemical stability of the material for application to an electrochemical device.
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`[O009]In addition, in the LH, Li2 S - X system, although a high ionic conductivity
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`of about 10-3 S / em is exhibited, a chernical stablity such as reductian of the sal
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`id electrolyte and decrease of conductivity due to contact with a lithium metalis n
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`ot solved, and there are many problems in the application development fo an elec
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`trachemical element such as an all-solid lithium battery.
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`[OO1O1Tt is an object of the presant invention to provide a lithium fon conducting
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`sold electrolyte and a method for its synthesis which have improved the prablem
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`of chemical stablity which leads to low conductivity or conductivity, which is a co
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`nventional problem.
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`{OO1L]
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`{Means for salving the problem] In the present Invention, a plurality of kinds of 1H
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`hiugn halide Z are mixed into an amorphous compound represented by a'lis PO
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`4 b’LI2S-c’ XK (where a’b‘c ‘is i and X is one or more sulfides selected fro
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`m the group of SiS2 ,GeS2 ,P2 55 ,682 53 }. A new amorphous lithium lon-conduc
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`ting solid electrolyte AM 3 PQ. sub. 4. BLi. sub. 2 S. multidet. cX. multidot. dZ is o
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`btained by heating and melting the mixture and then rapidly cooling. In this case,
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`abecdis 1, X is one or more sulfides selected frorm the group of a SIS2 ,GeS2 ,P2
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`$5 ,62 53, and Z is @ plurality of kinds of lithium halide, and an amorphouslithiu
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`m ion conductive solid electrolyte is used.
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`fOO12]in addition, the general formula AIL. sub. 3 PO. sub. 4. BLi. sub. 2 S. multi
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`dat. cX. multidot. dZ (where a+ bcdis 1 and X is one or more sulfides selected f
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`rom the group of SiS2Z ,GeS2 ,P2 55 ,B2 S3 3}. The amorphous lithium ion conduct
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`ive solid electralyte by which 2 is expressed with two or more type of [hium hall
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`des becomes thething excellent in especially chemical stability, when the sum of
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`the composition ratio a, b, and cis 0.9>=a+b+c>=0.4 and d is what fills 0.t<=<d
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`<=0.6.
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`(0013)
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`[Function]it is known that Li 3 PO 4 exhibits a crystal structure having high len co
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`nductivity in a high temperature region, but the structure is changed by phase tra
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`nsfer at around raom temperature, and ion conductivity is lowered.
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`[0014]However, it is considered that, by adding Li 3 PO 4 to a material which exh
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`ibits an amorphous state at room ternperature, and once amorphizing these mate
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`rials in a high-temperature state and then returning them to a room temperature
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`state, the state of Li 3 PO 4 can be maintained in an amorphaus state even at roa
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`m temperature, so that a high bonic conductivity can be obtained even at roam te
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`mperature,.
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`[O0i5]This is considered to be because, since the amorphous state, I. @., a struct
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`ure in which the arrangement of atoms of the crystal structure is somewhat disor
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`dered, unlike the crystalline material, lithium fons can move freely, so that ion co
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`nductivity is improved. In particular, a plurality of kinds of thium halide Z are mi
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`xed with an amorphous compound represented by a’Lis PO4 b’LI2S«c’ X (wh
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`ere a’ b’ec‘is i and Xis ane or more sulfides selected from the group of SiS2 ,
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`GeS2 ,P2 $5 ,B2 53). The mixture is heated and melted, and then rapidly coale
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`d, whereby a synthesized new amorphous lithium ion conductive solid electrolyte
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`AN 3 PO 4, BLi 2d S. cx. d2 (where abcdis 1 and X is one or more sulfides select
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`ed fram the group of Sis2 ,GeS2 ,P2 55 ,B2 S3 } is obtained. Z is a plurality of Ht
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`hilum hades which can move freely, and as a result, alis PO4 bLiI2 S- cf Kis
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`obtained. In this case, a lithium ion conductive solid electrolyte has a higher ion ¢
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`anductivity than an amorphous compound material represented by a’ b ‘cc’, whe
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`reina ’b’oc’is 1 and X is one or more sulfides selected framthe group of SIS2 ,
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`GeS2 ,P2S5 253.
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`[0016]
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`[Examples] In the lithium fon conductive solid electrolyte of the present inventic
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`n, an amorphous compound represented by a’Li3 PO4 B’LI2 5S -c’ X (where a’
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`b’ cis 1 and X is one or more sulfides selected fram the group of SiIS2 ,GeS2 ,P
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`255 ,B2 S3 ) is used as a base material. A plurality of kinds of lithium Halide 2 th
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`ere, Z=LiT,LIC] or LIBr} is used as the campound to be added. Since the amorpho
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`us campaund as a base material and the raw material and the synthesized solid e
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`lectrolyte are aasily decomposed by oxygen and moisture in the atmosphere, allo
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`Fthe handling is performed in a dry box under a dry argon atmosphere.
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`(QO17]in this case, iRhium halide was used, and all the reagents used were used,
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`and in particular, LIT, LIC] and the like were used after being dried at 400 ° C. for
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`6 hours under reduced pressure.
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`[0018 ]Hereinafter, the present invention wil be described in more detail with refe
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`rence to specific examples.
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`(Example 1) The inside of the amorphouslithium ion conductive solid electralyte
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`by the present invention, aLisPO4 and bLi2z S-cSi
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`An example of an amorphous lithium ion conductive solid electrolyte AIT 3 PO 4. 8
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`Li2 5 ><i$f 2- dZ using a S$ 2.amorphous material is described below.
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`([OO19]First, b “LI2S-c% Sis 2 fb “c= 1) was synthesized. This synthesis in
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`volves mixing lithium sulfide (Li 25) and silicon sulfide (Sis 2) into a b’=0.3-0.3.
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`The mixed powder was placed in a glassy carbon crucible, which was melted and
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`reacted at 950 ° €,
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`for 1.5 hours in an argon stream, and then poured into liquid
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`nitrogen to rapidly cool, thereby obtaining b“Li2S-c" Sis 2(b“c7” = 4).
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`[GOZO]Then, it is pulverized, Uthiurn phosphate {LI 3 PO 4) is added in a a‘LiS PO
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`4 b°LiI2S-c' Sis 250 as to be a a'=0.01-0.3, mixed, and the powder is put in
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`a glassy carbon crucible. After being melted and reacted at 950 ° C. far 1.5 hours
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`int an argon stream in an argon stream, the mixture was poured into quid nitrog
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`en and rapidly cooled to synthesive a’Li3 PO4 b’LI2 S.c'’ SIS 2 (a’+b'+c’=1).
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`(OO22j]A mixture of ithium fodide (LIT} and Itthium chloride (LICI) in @ ratio of 0.7:
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`0.3 is taken as a plurality of kinds of lithium halide 2 for the amount of the obtain
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`ed @lLi3 POS b’Li2 S+c’ Is 3 material y. After mixing such that y dis 1, the mi
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`xed powder was placed in a glassy carbon crucible, which was melted and reacted
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`at 950 ° C. in an argon stream for 1.5 hours, and then charged into liquid nitroge
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`n to rapidly cool the mixture, thereby obtaining AIT 3 PO 4. BLI 2S. ciS 2. dz {a+
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`bed= 2).
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`[O022]To investigate the characteristics of the synthesized safid electrolyte, ion c
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`onductivity was measured by an AC impedance method.
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`[OO23]The results obtained are shown in FIG. 1. A vertical axis represents an ion
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`conductivity, and @ horizontal axis represents an addition amount (mol%) of a plu
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`rality of types of lithium halide Z (where Z is a mixture of lithium iodide (LIT) and
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`lithium chioride (LICH) 0.7:0.3) for (G.03L13 PO4 - 6.58 LI2S- 0.39 is 2). FIG. 1
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`shows that the ionic conductivity increases with the addition of lithium halide Z, a
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`nd then decreases via the maximum, and the janic conductivity becomes largest.
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`0.75 (0.03Li3 PO4 - 0.58 LI2 5 - 0.39 is 2) - 0.25 (0. 7L1,0.3LICl), and its ion con
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`ductivity was 2.3 x 10-3 -S / em.
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`fO024]0n the other hand, the ionic conductivity of the 6.03113 PO4 G58 LI2S-
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`0.39 Is 2 to which no lithium halide was added was 7 x 10-4 -S5 / ecm,
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`([Q025]in order to investigate the chemical stability of an electrolyte to lithium me
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`tal, an electrolyte of various compositions synthesized is prepared.
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`A disk 1 having a thickness of 0.5 and a diameter-of 10 was press-molded, and a
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`lithium metal disk 2,2 “was pressed onto both surfaces of the disk 1 te form a se
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`aled cell 3 as shown in FIG. 2. In the chemical stability, the sealed cells 3 were st
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`ored in a thermostatic bath at 60 ° C. fer 500 hours, and a change in the internal
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`impedance of each sealed cell 3 with time was measured.
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`[OO2Z6]FIG. 3 shows the results obtained, and the vertical axis shows the impedan
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`ce change normalized by the internal impedance before storage. As is apparent fr
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`om this result, th was found that when the lithium halide is 0.6 or more, the chan
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`ge of the internal impedance with time becomes extremely large, and when it is |
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`ess than that, the increase of the internal impedance is small,
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`[0027 ](Example 2) it sets In Example 1 ~-- although the mixture of 0.7:0.3 of Hthi
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`um iodide (LII} and a lithium chioride (LIC!) was used to a'Li3 PO4 and the amou
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`nt af DLiZ S-c’SiS2 material y as two or mare type lithium halide Z to add Here,
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`AGL sub. 0.75 #O. sub. 4. BLi. sub. 2S. multidot. cSis. sub. 2. dZ fa+ bed = 1)
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`was obtained in the same manner as in Example 1, except that a mixture of Hithiu
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`mjodide (Lil). sub. 3: lithium bromide CLIBr}, sub. 0.25 was changed to an amou
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`nt of d.
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`([OO28]Ta investigate the characteristics of the synthesized solid electrolyte, fon ¢
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`onductivity was measured by an AC impedance method.
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`[0029]The results obtained are shawn in FiG. 4. A vertical axis represents an ion
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`conductivity, and a horizontal exis represents an addition amount (mol%)} of 4 plu
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`rality of kinds of lithium halide Z (where Z is a mixture of lithium iodide {Li} and i
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`ithium bromide (LiBr}) for (O.03Li3 PO4 - 0.58 Li 2S - 0.39 is 2) for( Li2S - O.
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`75:0.25 is}. FIG. 4 shows that the ionic conductivity increases with the addition o
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`flithium halide 2, and then decreases via the maximum, and the ianic canductivit
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`y¥ becomes largest. 0.90 (0.03Li3 PO4 - 0.58 Li2S - 0.39 is 2} - 6.20 (0.7510.
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`25LiBr}, and its ion conductivity was 2.6 x 10-3 - 5S / cm.
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`(DOSO](Exampie 3) it sets in Exarnple 1 -- although the mixture of 0.7:0.3 of Hthi
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`um iodide (LID) and a lithium chloride (LIC!) was used to a‘LiS PO4 and the amou
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`nt of b'LI2 S-c'SiS? material y as two or more type lithium halide 2 ta add Here,
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`AN 3 PO 4, BlLi2S. cS 2. dZ (a+ bed = 1} was obtained in the same manner as
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`in Example i, except that a mixture of lithium iodide (LIT} 0.7 : lithium bromide
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`(LIBr) 0.4: Nthium chloride (LICH) 0.2 was changed to an amount of d.
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`fOO3L]¥o investigate the characteristics of the synthesized solid alectrolyte, ion c
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`onductivity was measured by an AC impedance method.
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`[OQ032]Theresults obtained are shawn in FIG. 5. The vertical axis shows ion cond
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`uctivity, and the horizontal axis shows a plurality of types of lithium halide for (0.
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`O3Li3 PO4 - 0.58 LI2S > 0.39 is 2). In addition, 2 represents an addition amount
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`(mol®)} of lithium fodide (LH) 0.7, lithium bromide (LiBr) 0.1, and fithhim chloride
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`(LICH) 0.2. FIG. 5 shows that the ionic conductivity increases with the addition of I
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`ithium halide 2, and then decreases via the maximum, and the ionic conductivity
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`becomes largest. 0.80 (0.03Li3 PO4 - 0.58 Li 2S «0.39 is 2) > 0.20 (0. 7LH,O.1Li
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`Br,O.2LiICh, and its ion conductivity was 1.8 « 10-3 -S fem.
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`[O033]Example 4 describes an amorphous lithium ion conducting salid electrolyte
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`AN 3 PO 4. BLI2 S. cGeS 2. dZ using an AIT 3 PO 4. BLi 2S. cGeS 2 system amor
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`phous material.
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`fO0341First, 0.6 Li. sub. 2S. 0.4 GeS. sub. 2 glass was first synthesized as in Exa
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`mple 1. Specifically, ithiurn sulfide (Li 2 S} and germaniumsulfide (GeS 2) were
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`rixed at a molar ratio of 3:2, and the material powder was placed in a glassy car
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`bon crucible, which was reacted in an argon stream at 950 ° C. for 1.5 hours, and
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`then charged into liquid nitrogen and rapidly cocled to synthesize a material havi
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`ngaO.6li2aS- 0.4 GeS 2 composition. Subsequently, the material 0.6 Li. sub. 2
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`S. 0.4 GeS. sub. 2 thus obtained was ground, and lithium phosphate (Li. sub. 3 P
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`G. sub. 4) was mixed in a molar ratio of 97:3, and the powder was placed in a gis
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`ssy carbon crucible and reacted in an argon stream at 955. degree. C. for 1.5 hou
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`rs. Thereafter, it was poured into Hquid nitrogen and quenched to synthesize an a
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`morphous material represented by 0.03LI3 PO4 O.58 LiI2 5-00.39 Ges 2.
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`[O035]A mixture of lithium iodide {LID and lithium chloride (LIC in a ratio of 0.8:
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`0.2 as a plurality of kinds of lithium halide 2 is taken as ad amount of the obtain
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`ad 0.03LiI3 PO4 6.58 Li 2 S. 0.39 GaS 2 material y. After mixing such that y d wa
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`s i, the material powder was placed in a glassy carbon crucible, which was melte
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`d and reacted at 950 ° C. for 1.5 hours in an argon stream, and then charged int
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`o quid nitrogen to be rapidly coaled to obtain AIT 3 PO 4- BLI2S -cGeS 2+ dzZ
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`{a+ bed = 1).
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`fOO36]in order to examine the characteristics of the solid electrolytes of various c
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`ampasitions synthesized, lon conductivity was measured by an AC impedance me
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`thod.
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`[O037]Theresults obtained are shown in FIG. 6. A vertical axis represents an ion
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`conductivity, and a horizontal axis represents an addition amount (mols) of a plu
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`rality of kinds of lithium halide 2 to (Q.Q3Li3 PO4 - 0.58 Li2S «0.39 GeS 2}. FI
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`G. 6 shows the ion conductivity of lithium halide Z.
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`After increasing with the addition, it has been shown that there is a decraase via
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`a meximum, and the jonic canductivity is greatest. 0.85 (O.Q3UiI3 PO4 . multiiot.
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`0.58 LU. sup. 2S. multidot. 6.39 GeS. sup. 2). multidot. 0.15 (O.8LI,0.2LiC}), and
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`its jon conductivity value was 1.2. times. 10-3. sup. -S/ cm.
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`{[0038]Onthe other hand, theionic conductivity of the 0.03113 PO4 O.SELI2S -
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`0.39 GeS 2 to which no lithium halide was added was 2.0 x 10-4 -S / cm.
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`[O039]Next, the chemical stability of the electrolyte against lithium metal was ex
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`amined in the same manner as in Example 1.
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`[O040]As in Example 1, it was found that, with respect to the obtained result, ac
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`Range in the internal impedance with time significantly increases when the lithiu
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`m halide is at feast 0.6, and an increase in internal impedance decreases below th
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`at.
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`[O041](Exampie 5} it sets In Example 4 ~-- although Hthium iodide CLIT} and a Hthi
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`um chioride (LICH) used the mixture of 0.8:0.2 to a'Lid PO4 and the amount of
`
`b'Li2 S-c'GeS2 material y as two or more type lithium halide 4 to acid Here, AIL. s
`
`ub. G.7S PO, sub. 4. BL sub. 2S. cGeS. sub, 2. dz (a+ bed = 1) was obtained j
`
`n the same manner as in Example 4, except that a mixture of Hthium iodide (LIT).
`
`sub. 3: lithium bromide (LiBr}. sub. 0.15 : Ethium chloride (LICH. sub. G.1 was c
`
`hanged to an amount of d.
`
`(0042 ]Ta investigate the characteristics of the synthesized solid electrolyte, fon ¢
`
`onductivity was measured by an AC impedance method.
`
`[0043]fheresults obtained are shown in FIG. 7. The vertical axis indicates ion co
`
`nductivity, and the horizontal axis indicates a plurality of types of lithium halide F
`
`or (O.Q3L13 PO4 - 0.58 Li2S - 0.39 GeS 2}. In addition, 2 represents an addition
`
`amount (mal%) of lithium lodide (LI) 6.75, ithiurn bromide (LiBr) 0.15, and fithi
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`um chioride (LICH G.1. FIG. 7 showsthat the ionic conductivity increases with the
`
`addition of lithtum halide Z, and then decreases via the maximum, and the lonic c
`
`onductivity becomes largest. 0.75 (0.03L13 PO4 . multidot. 0.58 Li. sup. 2 5. mult
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`idot. 0.39 GeS. sup. 2}. multidot. 0.25 (0.75Li1,0. 15LiBr,O.20LICI), and its ion con
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`ductivity value was 1.1L. times. 10-3. sup. ~ Sf cm.
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`[O044]Example 6 describes an example of an amorphous Hthium ion canducting s
`
`oid electrolyte AIT 3 PO 4. BLI2S.cP25 5. dZ using an All 3 PO 4. BLI2 5. cP 2
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`S 5 system amorphous material.
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`[O0451First, 0.67 Li. sub. 2S. O.33P2 S5 glass was first synthesized as in Examp
`
`le 4. That is, the molar ratio of lithium sulfide (Li 2S) and phosphorus sulfide (P 2
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`S 5} is as follows :
`
`After mixing 2:1, the material powder was placed in a vitreous carbon crucible an
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`d reacted at 500 ° C. for 12 hours in an argon stream, followed by a reaction at 3
`
`090° ¢. for 2 hours, and then the mixture was poured into liquid nitrogen and rapi
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`dly cooled to synthesize a material having a composition of 0.67 Li2 S-O.33P25
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`5 . Subsequently, the material 0.67 Li. sub. 25. Q.33P2 S5 thus obtained was gr
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`ound, and lithium phosphate (Li. sub. 3 PO. sub. 4} was mixed in a molar ratio of
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`97:3, and the powder was placed in a glassy carbon crucible and reacted in an ar
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`gon stream at 950. degree. C. far 1.5 hours. Thereafter, it was poured into Hquid
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`nitregen and quenched to synthesize an amorphous material represented by 0.03
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`LIS PO4 0.651125. 0.32P2 $5.
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`[O046]A mixture of lithium lodide (LUD) and lithium chioride GUC} at a ratio of 0.7:
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`0.3 is taken as a plurality of types of lithium halide 2 for the amount of the obtain
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`ed 0.03LI5 PO4 0.65 Li 2 S. O.32P2 55 meterial y. After mixing such that y dis
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`1, the mixed powder is placed in a glassy carbon crucible, which is melted and re
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`acted at 950 ° C.
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`in an argon strearn for 1.5 fours, and then charged into liquid n
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`itrogen to rapidly cool it ta obtain AIT 3 PO4-BLIZ2S-cP255-dZfat+bed=
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`1}.
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`{0047 Jin order to examine the characteristics of the solid’ electralytes af various c
`
`ompositions synthesized, measurement of ion conductivity by an AC impedance
`
`method and chemical stability of the solid electrolyte to lithium metal were exami
`
`ned,
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`(O048] The results obtained are shown in FIG. 8. A vertical axis represents ion con
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`ductivity, and a horizontal axis represents an amount (mol®o} of a plurality of lithi
`
`um halide Cithium todide, lithium chloride mixture) added to (Q.03LI3 PO4 - 0.65
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`Li 2S -0.32P2 55 }. The composition having the largest ion conductivity was 0.7
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`5 (0.0313 PO4 - 0.65 L125 - 0.32P2 S5 } + 0.25 (0.7Li1,0.3LICI), andits ton con
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`ductivity value was 1.2 «x 10-3 -S /cm.
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`[0049]Onthe other hand, the ionic conductivity of the G.03L13 PO4 0.65 Li2S-
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`0.32P2 S5 to which no lithium halide was added was 4.2 x 10-4S /-om.
`
`(O050]Next, the chemical stability of the electrolyte against lithium metal was ex
`
`amined in the same manner as in Example 1.
`
`fOOSLIAs in Example i, it was found that, in the obtained results, a change in the
`
`internal impedance with time rernarkably increases when a plurality of lithium hall
`
`das is at least 0.6, and an increase in the Internal impedance decreases below tha
`
`t.
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`fO0S52]iIn Example 7, lithiurn iodide (Li) and Nthium chloride (LiCl) are added as p
`
`lural kinds of ithiurn halide Z to be added to the amount of the a'Li3 PO4 b’H 2
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`S-c’p2sS85 material ¥ 6.
`
`A 0.7:0.3 mixture was used, but in the same manner as in Example 6, a mixture
`
`of lithium iodide (Lil) G.75, lithium bromide (LIBr) 0.1, and Hthiumchloride (LIC)
`
`0.15 was changed to an amount of d. ALISPO4, bli2 S-cP2 55, and dZ (at+b+c+d
`
`=L) were obtained.
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`[QOS53TTo investigate the characteristics of the synthesized solid electrolyte, maas
`
`urement of jon conductivity by an AC impedance method was performed.
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`(0054]Theresults obtained are shown in FIG. 9. The vertical axis represents ion c
`
`onductivity, and the horizontal axis represents a plurality of types of Hthtum halid
`
`@ for (0.03Li3 PO4 > G.65 L125 -0.32P2 55 }. In addition, Z represents an additi
`
`on amount (mol%e)} of lithtum iodide (L172) 0.75, lithium bromide (LiGr} 0.1, and fit
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`hium chioride (LICH O.15. FIG. 9 shows that the lonic conductivity increases with
`
`the addition of lithium halide Z, and then dacreases via the maximum, and the fo
`
`nic conductivity becornes largest. 0.85 (0.01LI3 PO4 . multidot. 0.64 Li. sup. 2 5.
`
`multidot. Q.35P2 S5 ). multidot. 0.15 (O.95L,0. 1LIBr,O.TSLICH, and its fon condu
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`ctivity value was 1.7. times. 10-3. sup. S /f cm.
`
`fOOSSIFIG. & illustrates an example of a lithium ion conductive solid electrolyte Al
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`13 PO 4. BLi2 &. CB 2S. cB using an AIT 3 PO 4. BLi 2 5. cB 25 3 system amorp
`
`hous material, 3.
`
`fOOSS1First, O.5SLi2 S and 0.5 B-2 $3 glass was synthesized like Example 1 first. T
`
`hat is, Hithiurm sulfide (Li 2 5} and boron sulfide (8 2 5 3) are mixed at a molar rat
`
`io of 1:1. The material powder was piaced in a glassy carbon crucible, which was
`
`reacted at 500 ° C. for 12 hours in an argon stream, followed by a reaction at 80
`
`0° C, for 3 hours, and then poured into liquid nitragen to be rapidly coaled to syn
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`thesize a material having a composition of OU.5 Li25-0.5 B25 3. Then, material
`
`O.5Li2 S and 0.5 B-2 S35 obtained in this way were ground, Hthium phosphate (Li3
`
`P O04} was mixed to 96:4 by the mole ratio, the powder was put in glassy carbon
`
`crucible, and it was made to react by 800 degreein argon air current C for 3 hour
`
`s. Thereafter, it was poured into liquid nitrogen and quenched to synthesize an a
`
`morphous material represented by 0.G4LI3 PO4 O.48 LI2 S. 0.48B2 $3.
`
`(O057]A mixture of thium iodide (LIT} and lithium chioride (LIC!) at a ratio of 0.6
`
`5:06.35 is taken as a plurality of types of lithium halide Z for the arnount of the ob
`
`tained G.04L13 PO4 0.48 Li 2S. O.48B2 53 material y. After mixing so that y db
`
`ecames 1, the mixed powder is placed in a glassy carbon crucible, and the mixtur
`
`@is melted and reacted at 800 ° C in an argon stream for 1.5 hours, and then is
`
`put inte liquid nitrogen and rapidly cooled, and All 3 PO 4. BLi2a S. cB 25 3, dz
`
`(a+ bcd) is obtained.
`
`L} was obtained.
`
`fOOSSTin order to examine the characteristics of the solid electrolytes of various'¢
`
`ompositions synthesized, measurement of jon conductivity by an AC impedance
`
`method and chemical stability of the solid electrolyte ta Uthium rnetal were exami
`
`ned.
`
`fO059 The results obtained are shown in FIG. 10... The vertical axis indicates ion c
`
`onductivity, and the horizontal axis indicates the amount (mol%) of the Hithium h
`
`alide to be added to (G.04Li3 PO4 -Q.48Li2S5 - 0.4862 53 }. The composition h
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`aving the largest ion conductivity was 0.75 (G.03L13 PO4 - 0.65 Li 2S -0.32B2S
`
`3 }- 6.25 (0.65L31,0. 35LICH, and its ion conductivity value was 1.6 x 16-3-S/c¢
`ret.
`
`[O060j]Onthe other hand, the jon conductivity of the O.03Li3 PO4 / O.65 Li 2S -
`
`0.32B2 S3 without addition of a plurality of types of lithium halide was 3.0 « 10
`
`-4S5 / cm.
`
`{O061]Next, the chemical stability of the electrolyte against lithium metal was ex
`
`amined in the same manner as in Example 1.
`
`[O062]AS in Example i, tt was found that, in the obtained results, a change in the
`
`internal impedance with tirne significantly increases when the addition amount of
`
`the plurality of kinds of the hafagen lithium is 0.6 or more, and an increase in the
`
`internal impedance is small below that.
`
`fo063]
`
`[Effect of the Invention] The lithium fon conductive solid electrolyte of the presen
`
`t invention is abtained by adding a mixture of a plurality of types of lithium halide
`
`sto ali3 PO 4. Li2 S. K (X is one or more sulfide selected fram the group of SiS
`
`2 ,GeS2 ,P2S5 ,B2 S3 } sulfide-based sulfide amorphous materials. It is possible
`
`to provide a solid electrolytic material which exhibits higher lithhum ion conductivi
`
`ty and less chemical change depending on the contact of lithium metals as compa
`
`red with a base material of Li2 5 -*K (X is ane or more sulfides selected from the
`
`group of SiS? ,GeS? ,P? S5 ,B2 S3 }.
`
`[OO64 As a result, even whenthe lithium jon conductive selld electralyte is used a
`
`5 anelectrolyte for an electrochemical element such as a battery,.a capacitor, an
`
`electrachromic display element, and the like, it is expected that an electrochemic
`
`ai elament having high practicality can be manufactured.
`
`[O06S]in addition, in the synthesis of the solid electrolyte accarding to the embod
`
`iment of the present invertion, an amorphous material is successively synthesize
`
`d to obtain the desired lithium ion conductive solid electrolyte of the present inve
`
`ntion. In each case, it is obvious that the present invention can be simplified by 5
`
`electing various conditions such as an electrolyte composition, a synthesis temper
`
`ature, and a termperature increase condition. Although a single type of halide is u
`
`sed as a mixing ratio of a plurality of kinds of halides, an lon conductive solid elec
`
`trolyte can be obtained evan at a mixing ratio of other types. Therefore, * of the
`
`mixing ratio of other composition
`
`it goes without saying that the present invention also falis within the scope of the
`
`present invention.
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`
`
`(Brief Descrigtion of the Drawings]
`
`Fig. L]Characteristic curve showing the change in conductivity by the addition of
`
`a plurality of lithium halide (LH, LIC] mixture} to a°Li3 PO4 bb’ LIS S- cis 2.
`
`(Fig, 2]FIG. 1 is a cross-sectional view of a sealed cell used to measure internal j
`
`mpedance ;
`
`(Fig. 3]Characteristic of chernical Stability for Lithlurn Metal
`
`(Fig. 4]Characteristic curves showing the change in conductivity by the addition o
`
`fa plurality of lithium halides (LIT, LIGr mixtures} fo a’Li3 PO4 b’ LiI2 S.«c’ iS 2
`
`Fig. 5]Characteristic curve showing the change in conductivity by the addition of
`
`a plurality of lithiurn halide (@ mixture of LIU,LIBr, LiCl) to a'Li3 PO4 b’u 2 S-e’
`
`ig 2
`
`[Fig. 6]/Characteristic curve showing the change in conductivity by the addition of
`
`a plurality of lithium halide (LH, LIC] mixture) to aLi3 PO4 bb’ LIS S-o’ GeS 2
`
`Fig. 7]Characteristic curve showing the change In conductivity by the addition of
`
`& plurality of lithium halide (a mixture of LIL LIBr, Lich to a Lig PO4 bLiZG-c!'
`Ges 2
`
`[Fig. 8]Characteristic curve showing the change in conductivity by the addition of
`
`a plurality of lithium halide (LH, LiCi mixture} to alia PO4 bY’ Li2S-c'P2s5
`
`(Fig. 9]Characteristic curve showing the change in conductivity by the addition of
`
`a plurality of lithium halide (a mixture of LH, LIBr,LICD to a lis PO4 b’lu2S- ec!
`
`P2S5
`
`[Fig. L0]Characteristic curve showing the change in cond