HITTA NOUSUS 20180170756A1 ET UTAN MAN EI OLE A TOUT ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2018 /0170756 A1 SATO et al. ( 43) Pub . Date : Jun . 21 , 2018

(54 ) SOLID ELECTROLYTE PRODUCTION Publication Classification METHOD (51 ) Int. Cl. COIB 25 / 14 ( 2006 .01 ) (71 ) Applicant: Idemitsu Kosan Co ., Ltd ., Tokyo ( JP ) COIB 17 /22 ( 2006 . 01) ( 72 ) Inventors : Atsushi SATO , Ichihara - shi, Chiba COID 15 /04 ( 2006 .01 ) ( JP ) ; Minoru SENGA , Sodegaura -shi , HOIM 10 /0562 ( 2006 . 01 ) Chiba ( JP ) ; Masao AIDA , Ichihara -shi , HOIM 6 / 18 (2006 .01 ) Chiba ( JP ) (52 ) U . S . CI. ??? ...... COIB 25 / 14 (2013 .01 ); COIB 17 / 22 (73 ) Assignee : Idemitsu Kosan Co ., Ltd ., Tokyo (JP ) ( 2013 .01 ) ; COIP 2002 /72 ( 2013 .01 ) ; HOIM 10 /0562 (2013 .01 ) ; HOTM 6 / 18 (2013 .01 ) ; (21 ) Appl. No. : 15 /736 , 969 COID 15 / 04 ( 2013 . 01) ( 22 ) PCT Filed : Jun. 16 , 2016 (86 ) PCT No .: PCT/ JP2016 / 068011 (57 ) ABSTRACT $ 371 (c )( 1 ), The invention provides a method for producing a solid (2 ) Date : Dec. 15 , 2017 electrolyte , which includes reacting two or more kinds of Foreign Application Priority Data solid raw materials using a multi- axial kneading machine to (30 ) give a crystalline solid electrolyte , and which can provide a Jun . 17 , 2015 ( JP ) ...... 2015 - 122373 crystalline solid electrolyte with excellent productivity . 2 6a Sa 1 7a

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SOLID ELECTROLYTE PRODUCTION SUMMARY OF INVENTION METHOD Technical Problem TECHNICAL FIELD [0009 ]. However , the method relating to the invention described in PTL 1 includes two steps ofmechanical milling [0001 ] The present invention relates to a solid electrolyte treatment and mixing followed by heat treatment, and there production method . fore the process is often complicated . According to the method described in Comparative Examples 2 and 3 in PTL BACKGROUND ART 1 , a crystalline solid electrolyte could be obtained even [ 0002 ] With rapid spread of information - related instru though the mechanical milling treatment is not followed by ments, communication instruments and others such as per separate heat treatment, but the method could not be said to sonal computers , video cameras , cell phones and the like in be excellent in productivity . recent years , development of batteries that are utilized as [0010 ] The present invention has been made in consider power sources for them is considered to be important . ation of the situation as above , and its object is to provide a Heretofore, in batteries for such uses , an electrolytic solution method for producing a crystalline solid electrolyte excellent containing a flammable organic solvent has been used , but in productivity , as well as a multi - axial kneading machine . development of batteries having a solid electrolyte layer in place of an electrolytic solution is being made , which are Solution to Problem solid as a whole not using a flammable organic solvent [0011 ] The present inventors have assiduously studied for inside the batteries , in which , therefore , a safety unit can be the purpose of solving the above -mentioned problems and , simplified and which can drive down manufacturing costs as a result , have found that the problems can be solved by and are excellent in productivity . the following invention . [0003 ] As a solid electrolyte for use in the solid electrolyte [ 1 ] A method for producing a solid electrolyte , including layer , there is known an amorphous solid electrolyte or a reacting two or more kinds of solid raw materials using a crystalline solid electrolyte , which is adequately selected multi- axial kneading machine to give a crystalline solid depending on the use and the desired performance. Hereto electrolyte . fore , for producing a crystalline solid electrolyte , a method [ 2 ] The method for producing a solid electrolyte according of preparing an amorphous solid electrolyte by reaction of to the above [ 1 ], wherein the reaction is carried out in a solid raw materials according to a mechanical milling method , a state . slurry method , a melting and a rapidly cooling method or the [ 3 ] The method for producing a solid electrolyte according like followed by heat - treating the amorphous solid electro to the above [ 1 ] or [ 2 ] , wherein the solid raw materials lyte , and a method of reacting raw materials at a high contain a lithium element, a element and a sulfur temperature of 200° C . or so according to a mechanical element. milling method or the like have been employed ( for [ 4 ] The method for producing a solid electrolyte according example , PTL 1 ). The method of the invention described in to the above [3 ], wherein the solid raw materials contain at PTL 1 includes mechanically milling raw materials at 60° C . least one of a lithium compound and a lithium metal or higher and 160° C . or lower to give an amorphous solid elementary substance , and at least one of a phosphorus electrolyte and heat - treating it at 200° C . or higher and 360° compound and a phosphorus elementary substance . C . or lower to give a crystalline solid electrolyte . Compara [5 ] The method for producing a solid electrolyte according tive Examples 2 and 3 in PTL 1 disclose a process of to the above [ 3 ] or [ 4 ] , wherein the solid raw materials mechanically milling raw materials at a high temperature of contain lithium sulfide and phosphorus sulfide . 170° C . or 200° C . to give a crystalline solid electrolyte . [ 6 ] The method for producing a solid electrolyte according to any one of the above [ 3 ] to [ 5 ] , wherein the solid raw CITATION LIST materials further contain a halogen element. [ 7 ] The method for producing a solid electrolyte according Patent Literature to the above [6 ] , wherein the halogen element is at least one of and iodine . [0004 ] PTL 1 : JP 2010 -039889 A [ 8 ] The method for producing a solid electrolyte according to the above [6 ] or [7 ] , wherein the solid raw materials BRIEF DESCRIPTION OF DRAWINGS contain at least one of lithium and lithium iodide . [ 9 ] A method for producing an inorganic material, including 10005 ) FIG . 1 is a plane view cut at the center of a rotary reacting two or more kinds of solid raw materials using a shaft of a multi -axial kneading machine for use in the multi- axial kneading machine to give a crystalline inorganic present invention . material . [0006 ] FIG . 2 is a plan view cut vertically to the rotary [ 10 ] A multi - axial kneading machine for use in production of shaft in a part provided with paddles of the rotary shaft of the a crystalline solid electrolyte , the production including multi- axial kneading machine for use in the present inven reacting two or more kinds of solid raw materials . tion . [ 11 ] A method for producing a solid electrolyte , including reacting two or more kinds of solid materials containing [0007 ] FIG . 3 is an X - ray analysis spectrum of a crystal lithium sulfide and phosphorus sulfide , using a multi -axial line solid electrolyte obtained in Example 1 . kneading machine, to give a crystalline solid electrolyte [ 0008 ] FIG . 4 is an X - ray analysis spectrum of a crystal containing a lithium element, a phosphorus element and a line solid electrolyte obtained in Example 2 . sulfur element. US 2018 /0170756 A1 Jun . 21, 2018

[ 12 ] A method for producing a solid electrolyte , including DESCRIPTION OF EMBODIMENTS reacting two or more kinds of solid raw materials containing lithium sulfide , phosphorus sulfide , and at least one of [ Solid Electrolyte Production Method ] and lithium iodide , using a multi- axial [0013 ] The solid electrolyte production method of the kneading machine, to give a crystalline solid electrolyte present invention includes reacting two or more kinds of containing a lithium element, a phosphorus element, a sulfur solid raw materials using a multi- axial kneading machine to element, and at least one of a bromine element and an iodine give a crystalline solid electrolyte . element . [0014 ] In the present invention , the crystalline solid elec [ 13 ] A method for producing a solid electrolyte , including trolyte is a solid electrolyte material whose X - ray diffraction reacting two or more kinds of solid raw materials containing pattern in X - ray diffractometry gives a solid electrolyte lithium sulfide and phosphorus sulfide , using a multi - axial derived peak , irrespective of the presence or absence of solid kneading machine , to give a crystalline solid electrolyte electrolyte raw materials -derived peaks. Specifically , the containing a lithium element, a phosphorus element and a crystalline solid electrolyte contains a crystal structure sulfur element , wherein the temperature at the reaction is not derived from the solid electrolyte, in which a part of the lower than the crystallization temperature of the crystal crystal structure may be a crystal structure derived from the structure that the crystalline solid electrolyte has . solid electrolyte , or all the crystal structure may be a crystal [ 14 ] A method for producing a solid electrolyte, including structure derived from the solid electrolyte . With that, the reacting two or more kinds of solid raw materials containing crystalline solid electrolyte may partly contain an amor lithium sulfide , phosphorus sulfide, and at least one of lithium bromide and lithium iodide , using a multi -axial phous solid electrolyte so far as it has the above -mentioned kneading machine , to give a crystalline solid electrolyte X - ray diffraction pattern . containing a lithium element, a phosphorus element, a sulfur [0015 ] The above -mentioned amorphous solid electrolyte element, and at least one of a bromine element and an iodine is one whose X - ray diffraction pattern in X - ray diffractom element, wherein the temperature at the reaction is not lower etry is a halo pattern substantially not having any other peak than the crystallization temperature of the crystal structure than the materials - derived peaks, irrespective of the pres that the crystalline solid electrolyte has . ence or absence of solid electrolyte raw materials -derived [ 15 ] A method for producing a solid electrolyte, including peaks . reacting two or more kinds of solid raw materials containing lithium sulfide and disphosphorus pentasulfide using a ( Solid Raw Materials ) multi- axial kneading machine to give a crystalline solid [ 0016 ] With no specific limitation , the solid raw materials electrolyte containing a lithium element , a phosphorus ele for use in the production method of the present invention ment and a sulfur element. may be any ones that contain elements generally constituting [ 16 ] A method for producing a solid electrolyte , including crystalline solid electrolytes . For example , as the conductive reacting two or more kinds of solid raw materials containing species capable of expressing ion conductivity , at least one lithium sulfide, diphosphorus pentasulfide, and at least one element selected from alkalimetals such as lithium , sodium , of lithium bromide and lithium iodide , using a multi- axial potassium , rubidium , cesium , francium , etc . , and alkaline kneading machine, to give a crystalline solid electrolyte earth metals such as beryllium , magnesium , calcium , stron containing a lithium element, a phosphorus element, a sulfur tium , barium , radium and the like is preferred , and in element, and at least one of a bromine element and an iodine consideration of the ability of high ion conductivity and the element. ability to realize high output power of batteries , an alkali [ 17 ] A method for producing a solid electrolyte, including metal such as lithium , sodium , potassium , rubidium , cesium , reacting two or more kinds of solid raw materials containing francium , etc . , and beryllium aremore preferred , and lithium lithium sulfide and diphosphorus pentasulfide using a multi is especially preferred . Specifically, solid raw materials axial kneading machine to give a crystalline solid electrolyte containing at least one element selected from alkali metals containing a lithium element, a phosphorus element and a such as lithium , sodium , potassium , rubidium , cesium , fran sulfur element, wherein the temperature at the reaction is not cium , etc . , and alkaline earth metals such as beryllium , lower than the crystallization temperature of the crystal magnesium , calcium , strontium , barium , radium and the like structure that the crystalline solid electrolyte has . are preferred ; solid raw materials containing at least one [ 18 ] A method for producing a solid electrolyte , including element selected from an alkali metal such as lithium , reacting two or more kinds of solid raw materials containing sodium , potassium , rubidium , cesium , francium , etc . , and lithium sulfide , diphosphorus pentasulfide , and at least one beryllium are more preferred ; and solid raw materials con of lithium bromide and lithium iodide , using a multi- axial taining a lithium element are especially preferred. kneading machine , to give a crystalline solid electrolyte [ 0017 ] Any other element than the above -mentioned con containing a lithium element, a phosphorus element, a sulfur ductive species that may be in the solid raw materials may element, and at least one of a bromine element and an iodine be adequately selected in accordance with the kinds of the element , wherein the temperature at the reaction is not lower elements constituting the desired solid electrolytes . For than the crystallization temperature of the crystal structure example , the crystalline solid electrolytes include , as men that the crystalline solid electrolyte has. tioned below , oxide solid electrolytes , sulfide solid electro lytes , etc ., and in consideration of the ability to realize high output power of batteries , sulfide solid electrolytes are Advantageous Effects of Invention preferred . In this case , in consideration of the above -men [0012 ] According to the present invention , there can be tioned conductive species and of the purpose of obtaining provided a crystalline solid electrolyte with excellent pro crystalline sulfide solid electrolytes , the solid raw materials ductivity . are preferably those containing a lithium element, a phos US 2018 /0170756 A1 Jun . 21, 2018 phorus element and a sulfur element. Using such solid raw obtaining a crystalline solid electrolyte having high chemi materials , solid electrolytes containing a lithium element, a cal stability by employing a composition close to the ortho phosphorus element and a sulfur element corresponding to composition to be mentioned hereinunder , preferably within the elements contained in the solid raw materials are a range of 68 to 82 mol % , more preferably within a range obtained of 70 to 80 mol % , even more preferably within a range of [0018 ] As the solid raw materials containing a lithium 72 to 78 mol % , and especially more preferably within a element, at least one of lithium compounds such as lithium range of 74 to 76 mol % . sulfide ( Li, S ) , lithium oxide (Li20 ), lithium carbonate [0025 ] Also preferably, the solid raw materials further (Li , CO3 ), etc ., and a lithium metal elementary substance is contain at least one kind of halogen elements such as preferred ; and as the lithium compound , lithium sulfide fluorine ( F ) , chlorine ( C1) , bromine (Br ) and iodine ( I ) ,more (Li , S ) is especially preferred . preferably at least one of chlorine (C1 ), bromine ( Br ) and [0019 ] Any lithium sulfide may be used with no specific iodine ( I ) , even more preferably at least one of bromine (Br ) limitation , but one having a high purity is preferred . Lithium and iodine ( I ) . For example , a halogen - containing compound sulfide may be produced , for example , according to the represented by the following general formula ( 1) is prefer methods described in JP 7 - 330312 A , JP 9 - 283156 A , JP a bly contained . 2010 - 163356 A , and JP 2011 - 84438 A . [0020 ] Specifically , lithium hydroxide and hydrogen sul M -Xm ( 1) fide are reacted in a hydrocarbon -based organic solvent at 70 [ 0026 ] In the general formula ( 1 ) , M represents sodium to 300° C . to give lithium hydrosulfide , and then the reaction (Na ) , lithium ( Li) , boron ( B ) , aluminum ( Al) , silicon ( Si) , liquid is processed for hydrogen sulfide removal to give phosphorus ( P ), sulfur ( S ) , germanium (Ge ) , arsenic ( As) , lithium sulfide ( JP 2010 - 163356 A ) . Alternatively, lithium selenium (Se ) , tin (Sn ) , antimony ( Sb ) , tellurium ( Te ) , lead hydroxide and hydrogen sulfide may be reacted in a water (Pb ), bismuth ( Bi) , or those formed of the element with an based solvent at 10 to 100° C . to give lithium hydrosulfide , oxygen element and a sulfur element bonding thereto . and then the reaction liquid may be processed for hydrogen Lithium (Li ) or phosphorus ( P ) is preferred , and lithium (Li ) sulfide removal to give lithium sulfide (JP 2011 - 84438 A ). is especially preferred . [0021 ] In the absence of a solvent, lithium hydroxide may 0027 ] X represents a halogen element selected from fluo be reacted with hydrogen sulfide to give lithium sulfide . The rine ( F ) , chlorine ( CI) , bromine ( Br ) and iodine ( I ) . reaction temperature in this case is , for example , 20 to 300° [0028 ] 1 is an integer of 1 or 2 , and m is an integer of 1 to C ., 100 to 250° C ., or 120 to 240° C . 10 . When m is an integer of 2 to 10 , that is , when the formula [0022 ] As the solid raw materials containing a phosphorus has plural X ' s , X ' s may be the same or different . For element , for example , at least one of phosphorus sulfides example , regarding SiBrCl? to be mentioned below , m is 4 , such as diphosphorus trisulfide (P2S3 ), diphosphorus penta and X are different elements of Br and Cl. sulfide ( P . S . ) , etc . , silicon sulfide (Sis , ), germanium sulfide [ 0029 ] Specifically , examples of the halogen - containing (GeS2 ) , boron sulfide (B2S3 ) , gallium sulfide (Ga Sz) , tin compound represented by the above general formula ( 1 ) sulfide (SnS or Sns , ) , aluminum sulfide (Al , S . ) , zinc sulfide include sodium halides such as Nal, NaF , NaCl, NaBr, etc . ; ( ZnS ) , phosphorus compounds such as sodium phosphate lithium halides such as LiF , LiCl , LiBr, Lil, etc ., boron (Na3PO4 ) , etc ., and phosphorus elementary substance is halides such as BC13, BBrz , Biz, etc . , aluminum halides such preferred . The phosphorus compound is preferably a phos as AIF , AIBrz, Allz, AIC1z , etc . , silicon halides such as SiF4, phorus sulfide , and diphosphorus pentasulfide ( P2S3) is more SiCl4 , SiCl3 , Si Cl. , SiBr4 , SiBrCiz , SiBr2Cl2, Sile , etc . preferred . Phosphorus compounds such as diphosphorus phosphorus halides such as PF3, PF5 , PC13 , PC15, POC13 , pentasulfide (P2S3 ) and a phosphorus elementary substance PBrz , POBr3 , Plz, P2C14 , P214 , etc . , sulfur halides such as may be any ones that are industrially produced and com SF2, SF4, SF6, S2F10 , SC12, S2Cl2, S2Br2 , etc ., germanium mercially available , with no specific limitation for use halides such as GeF4 , GeCl4 , GeBr? , Gely , GeF2, GeCl2 , herein . GeBr2, Gel , etc ., arsenic halides such as AsF3, AsC1z , 0023] The solid raw materials containing a lithium ele AsBrz , Aslz , AsFs, etc ., selenium halides such as SeF4, SeFo, ment, a phosphorus element and a sulfur element preferably SeCl2 , SeC14 , Se Br2, SeBr4 , etc ., tin halides such as SnF4 , contain at least one of a lithium compound and a lithium SnC14 , SnBr4 , Sn14 , SnF2, SnCl2 , SnBrz, Snly , etc ., anti metal elementary substance , and at least one of a phosphorus mony halides such as SbF3, SbC1z , SbBrz , Sblz, SbFs, compound and a phosphorus elementary substance . Above SbC1z , etc ., tellurium halides such as TeF4, Te, F10 , TeF6, all , a combination of a lithium compound and a phosphorus TeCl2 , TeC14 , TeBrz, TeBr4 , Tels , etc ., lead halides such as compound is preferred , a combination of a lithium com PbF4, PbC14 , PbF2, PbCl2 , PbBr2, Pbly , etc . , bismuth halides pound and a phosphorus sulfide is more preferred , a com such as BiF3, BiClz , BiBrz , Bilz , etc . bination of a lithium sulfide and a phosphorus sulfide is even (0030 ] As the above -mentioned halogen - containing com more preferred , and a combination of a lithium sulfide and pound , lithium halides such as lithium chloride (LiCl ) , a diphosphorus pentasulfide is especially more preferred . lithium bromide (LiBr ) , lithium iodide (Lil ), etc ., and phos [0024 ] Not specifically limited , the amount of the lithium phorus halides such as (PC15 ) , element- containing solid raw materials and the phosphorus phosphorus trichloride ( PC13 ) , phosphorus pentabromide element -containing solid raw materials to be used may be (PBrz ), (PBrz ), etc . are preferred . adequately determined based on the desired crystalline solid Above all, lithium halides such as lithium chloride ( LiC1) , electrolyte . For example , when lithium sulfide (Li , S ) is used lithium bromide (LiBr ) , lithium iodide (Lil ) , etc ., and phos as the lithium element -containing solid raw material and phorus tribromide ( PBrz ) are preferred ; and lithium halides when diphosphorus pentasulfide (P2S3 ) is used as the phos such as lithium chloride (LiCl ) , lithium bromide (LiBr ) , phorus element - containing solid raw material, the ratio of lithium iodide (Lil ) , etc . are more preferred ; and lithium Li2S to the total of Li2S and P2S , is , from the viewpoint of bromide (LiBr ) and lithium iodide (Lil ) are especially US 2018 /0170756 A1 Jun . 21, 2018 preferred . As the halogen - containing compound , one alone slurry thereof with an organic solvent . In the present inven or two or more kinds of the above -mentioned compounds tion , in consideration of productivity and mass - productivity , may be used either singly or as combined . Namely , at least an organic solvent is used as little as possible , and using one of the above - mentioned compounds may be used . solid raw materials directly as they are , that is , using them [0031 ] For example , in the case where lithium bromide in a solid state is preferred in reaction . ( LiBr ) and lithium iodide (Lil ) are used as the halogen [0037 ] Depending on the kind of solid raw materials , containing compound, the total amount to be used of lithium production would be easy along with using an organic bromide (LiBr ) and lithium iodide ( Lil ) in the solid raw solvent. Examples of the organic solvent for use in such a materials for use for production of a crystalline solid elec case include an organic solvent having a boiling point of trolyte is not specifically limited so far as the ratio can give 200° C . or higher. Such organic solvents include dialcohols a desired crystalline solid electrolyte , but for example , the such as 1 , 2 -butanediol , 1 , 3 -butanediol , 1 , 2 -pentanediol , 1 , 3 amount preferably falls within a range of 3 to 40 mol % , pentanediol, 1 , 4 -pentanediol , 1 , 5 -pentanediol , 2 , 3 -pen more preferably within a range of 3 to 35 mol % , even more tanediol, 2 ,4 -pentanediol , 1, 2 -hexanediol , 1, 3 -hexanediol , preferably within a range of 3 to 30 mol % . For example , the 1 , 4 -hexanediol , 1 , 5 -hexanediol , 1 , 6 - hexanediol, and deriva amount may fall within a range of 5 mol % or more and 28 tives thereof, etc . In the present invention , one alone or two mol % or less , a range of 8 mol % or more and 28 mol % or more kinds of these organic solvents may be used either or less , a range of 10 mol % or more and 28 mol % or less , singly or as combined . a range of 12 mol % or more and 28 mol % or less , or a range [ 0038 ] In the case where an organic solvent is used , the of 15 mol % or more and 28 mol % or less . amount thereof to be used is preferably such that the total 10032 ] The proportion of lithium bromide ( LiBr ) to the amount of the solid raw materials to be added relative to 1 total of lithium bromide (LiBr ) and lithium iodide (Lil ) liter of the organic solvent could be 0 . 001 to 1 kg, more ( LiBr/ (LiI + LiBr )) is not specifically limited , and any desired preferably 0 . 005 to 0 . 5 kg, more preferably 0 . 01 to 0 . 3 kg. ratio may be employed , but the proportion is preferably such The amount of the organic solvent to be used is preferably that an Li ion conductivity not lower than the same level as small as possible. relative to the crystalline solid electrolyte ( crystalline solid electrolyte as a comparative subject) prepared in the same (Multi -Axial Kneading Machine ) manner except that lithium bromide ( LiBr ) is substituted [ 0039 ] The multi -axial kneading machine for use in the with lithium iodide (Lil ) could be obtained , and more production method of the present invention is , for example , preferably such that an Li ion conductivity higher than the provided with a casing and two or more rotary shafts comparative subject, crystalline solid electrolyte can be arranged to run through the casing in the longitudinal obtained . The proportion of the above -mentioned lithium direction and equipped with paddles (screw blades ) along bromide (LiBr ) is , for example , within a range of 1 to 99 mol the axial direction , in which one end in the longitudinal % , more preferably within a range of 5 to 75 mol % . For direction of the casing is provided with a supply port for example , the proportion may fall within a range of 20 mol solid raw materials and the other end is provided with a % or more and 75 mol % or less, or 40 mol % or more and discharge port, and the machine is not specifically limited in 72 mol % or less , or 50 mol % or more and 70 mol % or less . point of the other constitution . It is considered that , by [ 0033 ] Preferably , the proportion of lithium iodide (Lil ) in rotating the two or more rotary shafts provided with paddles all the materials for use in production of the crystalline solid in such a multi -axial kneading machine , two ormore rotary electrolyte is more than 3 mol % but less than 20 mol % , and movements may interact with each other to form shearing the proportion of lithium bromide (LiBr ) in all the materials stress , and the shearing stress may be imparted to the solid is preferably 3 to 20 mol % . raw materials moving from the supply port toward the [0034 ] In the case where the crystalline solid electrolyte discharge port along the rotary axis , and the raw materials has a composition of a ( ( 1 - b )Lil . bLiBr ). ( 1 - a ) ( cLi, S . ( 1 - c ) could be thereby reacted and crystallized . P2S3 ), a corresponds to the total proportion of the above 10040 ] One preferred example of the multi - axial kneading mentioned Lil and LiBr, b corresponds to the proportion of machine usable in the present invention is described with the above- mentioned LiBr, and c corresponds to the propor reference to FIGS . 1 and 2 . FIG . 1 is a plane view cut at the tion of the above -mentioned Li S . center of the rotary shaft of a kneading machine, and FIG . [0035 ] The particle size of the above -mentioned solid raw 2 is a plan view cut vertically to the rotary shaft in a part materials may be any particle size that each of the above provided with paddles of the rotary shaft . mentioned raw materials generally has with no specific 10041 ] The multi- axial kneading machine shown in FIG . 1 limitation . For example , the particle size of lithium sulfide is a biaxial kneading machine provided with a casing 1 may be 0 .01 to 3 mm , the particle size of diphosphorus provided with a supply port 2 at one end and a discharge port pentasulfide may be 0 .01 to 3 mm . The particle size of 3 at the other end , and two rotary shafts 4a and 4b arranged lithium bromide may be 0 .01 to 3 mm , and the particle size to run through in the longitudinal direction of the casing 1 . of lithium iodide may be 0 . 01 to 3 mm . In that manner, the The rotary shafts 4a and 4b each are provided with paddles particle size range of the solid raw materials for use in the 5a and 5b , respectively . Solid raw materials enter the casing present invention is broad , and using a multi - axial kneading 1 via the supply port 2 , and are reacted with each other and machine , a solid electrolyte can be produced irrespective of crystallized , as given shearing stress at the paddles 5a and the particle size of the solid raw materials . Here , the mean 5b , and the resultant reaction product, that is , a crystalline particle size is a value to be measured using a laser diffrac - solid electrolyte is discharged out via the discharge port 3 . tometric particle sizer (for example, Master Sizer 2000 [0042 ] Not specifically limited , the number of rotary manufactured by Malvern Instruments , Ltd . ) . shafts 4 (4a , 4b ) may be 2 or more, and in consideration of [0036 ] The above -mentioned solid raw materials may be general versatility , the number is preferably 2 to 4 , more used directly as they are , but may be used in the form of a preferably 2 . US 2018 /0170756 A1 Jun . 21, 2018

[0043 ] The rotary shafts 4 may be parallel shafts that are structure that the crystalline solid electrolyte has, that is , a parallel to each other , or may be oblique shafts , and the crystallization temperature of the amorphous solid electro rotating direction of the rotary shafts may be in the same lyte obtained using the solid raw materials necessary for direction or in different directions . For obtaining a better producing the crystalline solid electrolyte , and can be con kneading effect , the rotating direction is preferably in dif firmed and measured through differential thermal analysis ferent directions , or in the case where a self - cleaning effect (DTA ) . For example , using a differential thermal analyzer of sweeping up the solid raw materials and the reaction (DTA device ) , a sample is heated at a heating condition of product in the casing and preventing them from staying in 10° C . /min for differential thermal analysis (DTA ) , in which the casing is considered to be important, the same direction a temperature indicating the exothermic peak to be detected may be selected for the rotating direction . on the lowermost side is the crystallization temperature of [0044 ] Paddles 5 (5a , 5b ) are fixed to the rotary shafts for the sample . kneading solid raw materials , and are referred to as screw [0051 ] The crystallization temperature differs depending blades . Not specifically limited , the cross - sectional form on the kind and the compositional ratio of the elements thereof includes , as shown in FIG . 2 , a nearly triangle form constituting the resultant crystalline solid electrolyte and on modified from a regular triangle by making each side thereof the difference in the structure thereof, and , for example , the have a uniformly convexed arc , and in addition thereto , a crystallization temperature of the crystal structure that an circular form , an oval form , a nearly square form , etc . , and Li2S P2Sz- based crystalline solid electrolyte has falls , for may additionally include modifications based on these forms example , within a range of 210 to 340° C ., the crystallization and having a partial cutout. temperature of the crystal structure that an Li2S - P2S3 [0045 ] In the case where the machine is provided with LiBr -based crystalline solid electrolyte has falls , for plural paddles, each paddle may be fixed to the rotary shaft example , within a range of 170 to 290° C ., the crystallization at a different angle , as shown in FIG . 2 . The paddles may be temperature of the crystal structure that an Li2S - P2S3 engaging ones or non - engaging ones, but for obtaining a Lil - based crystalline solid electrolyte has falls , for example , better kneading effect , engaging paddles may be selected . within a range of 140 to 260° C . , and the crystallization [ 0046 ] For smoothly supplying solid raw materials there temperature of the crystal structure that an Li, s — P , S , into , the multi -axial kneading machine may be provided Lil — LiBr -based crystalline solid electrolyte has falls , for with screws 6 (6a , 6b ) on the side of the supply port 2 as example , within a range of 140 to 260° C . The reaction shown in FIG . 1 , and for preventing the reaction product temperature in producing these crystalline solid electrolytes obtained via the paddles 5 from staying inside the casing , may be one not lower than the crystallization temperature of reverse screws 7 (7a , 76 ) may be arranged on the side of the the crystal structure that each solid electrolyte has. discharge port 3 as shown in FIG . 1 . [0052 ] In the present invention , the reaction temperature [0047 ] A commercially -available kneading machine may is , from the viewpoint of obtaining a crystalline solid be used as the multi- axial kneading machine . Examples of electrolyte , preferably one not lower than the above -men commercially - available multi -axial kneading machines tioned crystallization temperature , and the specific tempera include KRC Kneader, KRC Junior (manufactured by ture could not be indiscriminately defined since , as men Kurimoto , Ltd . ) , etc . , and depending on the kinds of solid tioned above , the crystallization temperature varies raw materials and on the desired scale , the machine may be depending on the kind and the compositional ratio of the adequately selected . constituent elements and on the difference in the structure [ 0048 ] For producing a crystalline solid electrolyte , a thereof. For example, the reaction temperature is preferably method of preparing an amorphous solid electrolyte accord 120 to 350° C . , more preferably 130 to 320° C ., even more ing to a mechanical milling method , a slurry method , a preferably 140 to 280º C . , and especially preferably 150 to melting and rapidly cooling method or the like as described 250° C . above followed by further heat- treating the resultant amor [0053 ] As a method for controlling the reaction tempera phous solid electrolyte has heretofore been generally ture for solid raw materials , a method generally used in a employed . These methods could not be said to be excellent multi- axial kneading machine may be employed . For in productivity since they require a special equipment or example , the method includes a method of controlling the must use a hydrocarbon - based organic solvent. However, by supply amount of solid raw materials , a method of control reacting solid raw materials using a generalized machine ling the driving power , a method of controlling the rotation such as a multi- axial kneading machine as in the present number, a method of cooling the system , etc . In the method invention , excellent productivity could be realized , as com of controlling the supply amount of solid raw materials , in pared with these production methods . general, when the supply amount is increased , the tempera ture tends to rise . In the method of controlling driving (Reaction Conditions) power , in general, when the driving power is increased , the [0049 ] In the present invention , the reaction temperature temperature tends to rise . In the method of controlling the for the solid raw materials is preferably not lower than the rotation number , in general, when the rotation number is crystallization temperature of the crystal structure that the increased , the temperature tends to rise . crystalline solid electrolyte obtained by the reaction of the [0054 ] The rotation number of the rotary shaft of the solid raw materials has. By the reaction at such a tempera multi- axialkneading machine differs , depending on the kind ture , the solid raw materials can be reacted and crystallized and the compositional ratio of the elements constituting the to give a crystalline solid electrolyte , and therefore the crystalline solid electrolyte to be produced and on the intended solid electrolyte can be obtained with excellent difference in the structure thereof, and therefore could not be productivity . indiscriminately stated , but is preferably 40 to 300 rpm , [0050 ] Here , the crystallization temperature in the present more preferably 40 to 250 rpm , even more preferably 40 to invention is a crystallization temperature of the crystal 200 rpm . US 2018 /0170756 A1 Jun . 21, 2018

[0055 ] For obtaining the crystalline solid electrolyte, as minute or more and 24 hours or less , more preferably within needed , a jacket heater (hot water heater, electric heater ) or a range of 1 minute or more and 10 hours or less. the like may be used to heat the reactor for raw materials 10063 ] Preferably , the heat treatment is carried out in an such as the casing or the like of the multi- axial kneading inert gas atmosphere ( for example , nitrogen atmosphere , machine . argon atmosphere ), or in a reduced -pressure atmosphere [ 0056 ] Regarding the reaction of solid raw materials , the ( especially in vacuum ) . This is because the crystalline solid crystalline solid electrolyte to be obtained may change when electrolyte can be protected from degradation ( for example, brought into contact with water or oxygen , and therefore , oxidation ) . The heat treatment method is not specifically supply and reaction of the solid raw materials as well as limited . For example , a method of using a vacuum heating discharge of the reaction product are preferably carried out device , an argon gas atmosphere furnace , a firing furnace or in an inert gas atmosphere . In this case , the inert gas includes the like may be employed . nitrogen , argon , etc . [0057 ] Also preferably , the reaction of solid raw materials (Crystalline Solid Electrolyte ) is carried out in a dry atmosphere , for example , preferably [0064 ] The crystalline solid electrolyte obtained according in an atmosphere at the dew point - 90° C . or higher and to the production method of the present invention includes - 40° C . or lower, more preferably in an atmosphere at the a crystalline solid electrolyte that contains , for example , at dew point - 90° C . or higher and - 45° C . or lower, even more least one element selected from alkali metals such as preferably at the dew point - 90° C . or higher and - 50° C . or lithium , sodium , potassium , rubidium , cesium , francium , lower. For realizing this , for example , a method of arranging etc ., and alkaline earth metals such as beryllium , magne the multi - axial kneading machine in a glove box , or a sium , calcium , strontium , barium , radium , etc . , as a conduc method of arranging the multi - axial kneading machine in a tive species . Among those elements , in consideration of the dry room may be employed . Also for example , a method of ability of high ion conductivity and the ability to realize high continuously supplying the above -mentioned inert gas into output power of batteries , an alkali metal such as lithium , the casing of the multi - axial kneading machine can realize sodium , potassium , rubidium , cesium , francium , etc . , and the above . In this case, the casing of the multi -axial kneading beryllium are preferred , and lithium is especially preferred . machine may be provided with a supply port and a discharge 10065 ] The crystalline solid electrolyte includes a crystal port for an inert gas. line oxide solid electrolyte , a crystalline sulfide solid elec [0058 ] The reaction time for the solid raw materials varies trolyte , etc . , and in consideration of the ability of high ion depending on the kind and the compositional ratio of the conductivity and the ability to realize high output power of elements to constitute the crystalline solid electrolyte to be batteries, a crystalline sulfide solid electrolyte is preferred . obtained , on the difference in the structure thereof, and on [0066 ] Examples of the crystalline sulfide solid electrolyte the temperature at the reaction , and therefore may be include a crystalline sulfide solid electrolyte containing a adequately controlled . Preferably, the time is 5 minutes to 50 lithium element, a phosphorus element and a sulfur element, hours , more preferably 10 minutes to 15 hours, even more a crystalline sulfide solid electrolyte containing a lithium preferably 1 to 12 hours . element, a phosphorus element, a sulfur element and a [0059 ] In using the multi- axial kneading machine, the halogen element, a crystalline sulfide solid electrolyte con reaction product discharged out through the discharge port taining a lithium element, a phosphorus element , a sulfur may be again supplied thereinto through the supply port element and a bromine element, a crystalline sulfide solid depending on the degree of the reaction procedure to thereby electrolyte containing a lithium element, a phosphorus ele further carry out the reaction . The degree of reaction pro ment, a sulfur element and an iodine element, and a crys cedure may be known by the change of the peaks derived talline sulfide solid electrolyte containing a lithium element, from the solid electrolyte raw materials , and at the time a phosphorus element, a sulfur element, a bromine element when the peaks could be detected no more , it may be and an iodine element . More specifically , the crystalline considered that the reaction has fully proceeded . sulfide solid electrolyte includes Li , s — P , S . , Li , S - P , S , — Lil, Li2S - P2S5 - LICI, Li2S - P2S3 - LiBr, Li2S - P2S5 – (Heat Treatment) Lil — LiBr, LiS P2S3 - Li20 , Li, s — P , Sz - Li2O – Lil , [0060 ] In the present invention , from the viewpoint of LiSSiS2, , Li,SSiSz - Lil, Li,SSiS - LiBr, Li2S further improving the crystallinity of the crystalline solid SiSz - LiCI, Li, S — SiS2 - B2S3 - Lil , Li,S SiSz - P2S5 electrolyte obtained in the manner as above, heat treatment Lil, Li, S B S3, Li,S P Sz - ZmSn ( m and n each are a may be carried out. Specifically , the production method of positive number, Z represents any of Si, Ge , Zn , Ga , Sn , the present invention may further include heat treatment of Li s – GeS2, Li s — SiS2 - Li3PO4, Li,SSiS2 - Li, MO the crystalline solid electrolyte . ( x and y each are a positive number, M represents any of P , [ 0061] Theheat treatment temperature is preferably within Si, Ge , B , Al, Ga, Li GeP2S12 , etc . a range of + 40° C . from the peak top , as the origination , of [0067 ] The crystalline oxide solid electrolyte includes the exothermic peak detected on the lowermost temperature Li20 B203 - P205, Li20 - SiO2, LiLaTaO ( for example , side in differential thermal analysis (DTA ) at a heating LisLazTa2012) , LiLaZrO (for example , Li LazZr2012 ), condition of 10° C ./ min using a differential thermal analyzer LiBaLaTaO ( for example , Li_ BaLa Ta2012) , LiltzSipi (DTA device ) , for the amorphous solid electrolyte obtained 204 (0 < x < 1 , for example , Li3 .6S10 . 6P0. 404 ) , Lii +zAl , Ge2- x using the solid raw materials necessary for obtaining the (PO4 ) 3 (Osxs2 ), Li1 +xA1 Ti2 -r ( PO4) 3 (Osxs2 ), LizPO (4 -3 / 2x ) desired crystalline solid electrolyte , more preferably + 30° N , (0 < x < 1 ), etc . C . , even more preferably + 20° C . [0068 ] The kind of the elements constituting the crystal [0062 ] Not specifically limited , the heat treatment time line solid electrolyte obtained according to the production may be any time in which the desired crystallinity can be method of the present invention can be identified , for obtained but is , for example , preferably within a range of 1 example , by an ICP emission spectrometer. US 2018 /0170756 A1 Jun . 21, 2018

[0069 ] For example , the crystal structure of the crystalline a crystal structure that gives , in X - ray diffractometry using sulfide solid electrolyte includes an LizPS4 crystal structure , a CuKa ray , peaks derived from an Li — Si – P — S - type an Li P . S . crystal structure, an Li- PS , crystal structure, an crystal structure and appearing at 20 = 20 . 2°, 24 .0° , and Li- P2Su crystal structure , an Li4 - Ge _ P _ S4- based thio 29 . 7°, and peaks appearing at 20 – 24. 8° to 26 . 1º. These peak LISICON Region II - type crystal structure ( see Kanno , et al . , positions may vary within a range of + 0 .5º . Journal of The Electrochemical Society , 148 ( 7) A742 -746 [ 0075 ] The crystalline solid electrolyte obtained according ( 2001) ) , a crystal structure similar to the Li4 - Ge -XP _ S4 to the present invention preferably has a constitution that based thio -LISICON Region II - type crystal structure ( see contains an ion conductor having a lithium element (Li ) , a Solid State Ionics, 177 (2006 ) , 2721 - 2725 ) , etc . phosphorus element (P ), and a sulfur element ( S ) , more [ 0070 ] In X - ray diffractometry thereof using a CuKa ray, preferably a constitution that contains the ion conductor and the Li PS . crystal structure gives diffraction peaks , for lithium iodide (Lil ) and lithium bromide (LiBr ). example , at around 20 = 17. 5° , 18 .3° , 26 .1° , 27 .3° , 30 .0° ; the [0076 ] The above -mentioned ion conductor is not specifi Li_ P2S6 crystal structure gives diffraction peaks, for cally limited and may be any one having a lithium element example , at around 20 = 16 . 9° , 27. 1° , 32. 5° ; the Li PS6 (Li ) , a phosphorus element ( P ) and a sulfur element ( S ) . crystal structure gives diffraction peaks, for example , at Above all , the ion conductor preferably has an ortho com around 20 = 15. 3° , 25. 2° , 29. 6° , 31. 0° ; the Li- P2S11 crystal position . This is because the ortho composition can provide structure gives diffraction peaks , for example , at around a sulfide solid electrolyte having high chemical stability . 20 = 17. 8°, 18. 5°, 19. 7° , 21. 8° , 23. 7°, 25. 90 , 29. 6°, 30 . 0° ; the Here, in general, ortho means one having a highest hydration Li4 - rGe -XP _ S4 -based thio - LISICON Region II -type crystal degree among oxo -acids produced by hydration of a same structure gives diffraction peaks, for example , at around oxide . In the present invention , a crystal composition where 20 = 20 . 1° , 23 . 9° , 29. 5° ; and the crystal structure similar to lithium sulfide ( Li, S ) among sulfides mostly has been added the Li4_ Gel- P _ S4- based thio -LISICON Region II -type is referred to as an ortho composition . For example , in an crystal structure gives diffraction peaks , for example, at LiS , P . S system , Li PS , corresponds to an ortho compo around 20 = 20. 2 , 23 .6º . The position of these peaksmay vary sition . In the case where the crystalline sulfide solid elec within a range of + 0 .5º . trolyte is Li2S - P2S5 , the proportion of lithium sulfide [ 0071] The crystal structure of the crystalline solid elec (Li S ) to diphosphorus pentasulfide (P2S3 ) capable of form trolyte also includes an argyrodite -type crystal structure . ing an ortho composition is Li, S :P2S5 = 75 : 25 by mol. Examples of the argyrodite - type crystal structure include an [0077 ] Here , “ having an ortho composition ” includes not Li PS , crystal structure ; a crystal structure represented by a only a strict ortho composition alone but also compositions compositional formula Li7 - P1- Si, S6 or Li7 + xP1 _ , Si, S . ( x close thereto . Specifically , the wording indicates mainly the is - 0 . 6 to 0 .6 , y is 0 . 1 to 0 . 6 ) which has a structure skeleton anion structure ( PS43 - structure ) of the ortho composition . of Li , PSG and in which a part of P is substituted with Si; a The proportion of the anion structure in the ortho compo crystal structure represented by Liz - x - 2 , PS6- x - C1 sition is preferably 60 mol % or more relative to all the anion (0 .8sxs1 .7 , O < ys - 0 .25x + 0. 5) ; a crystal structure repre structures in an ion conductor, more preferably 70 mol % or sented by Li7 - PS6 _xHa , (Ha represents Cl or Br, x is more , even more preferably 80 mol % or more, still more preferably 0 . 2 to 1 . 8 ) . preferably 90 mol % or more . The proportion of the anion [ 0072 ] The crystal structure represented by a composi structure in the ortho composition may be determined tional formula Liz _ P1_ , Si, S . or Liq +xP1 - Si, S6 ( x is - 0 . 6 to through Raman spectrometry , nuclear magnetic resonance 0 .6 , y is 0 . 1 to 0 .6 ) , which has the above -mentioned structure (NMR ), X - ray photoelectron spectrometry (XPS ) or the like . skeleton of Li- PSG and in which a part of P is substituted [0078 ] Preferably , the crystalline sulfide solid electrolyte with Si, is a cubic crystal or a rhombic crystal, and is obtained as the crystalline solid electrolyte according to the preferably a cubic crystal, and in X - ray diffractometry using present invention does not substantially contain a cross a CuKa ray , the crystal structure gives peaks appearing linked sulfur. This is because the crystalline solid electrolyte mainly at 20 = 15 .5º , 18 . 0° , 25 .0° , 30 . 0° , 31 .4° , 45 . 3º , 47 . 0° , could be one with little hydrogen sulfide emission . “ Cross and 52. 0°. The crystal structure represented by the above linked sulfur” is a crosslinked sulfur in a compound pro mentioned compositional formula Li7 -x - 2, PS6 -x -- C1 duced by reaction of lithium sulfide ( Li , S ) and diphosphorus ( 0 . 8sxs1. 7 , 0 < ys - 0 .25x + 0 . 5 ) is preferably a cubic crystal, pentasulfide (PS3 ) . For example , the crosslinked sulfur in a and in X -ray diffractometry using a CuKa ray, the crystal structure S P - S - PS , formed by reaction of lithium sulfide structure gives peaks appearing mainly at 20 = 15. 5°, 18 . 0°, (Li2S ) and diphosphorus pentasulfide ( P2S3 ) corresponds 25 .0° , 30 . 0° , 31. 4° , 45 . 3°, 47 .0° , and 52 .0° . The crystal thereto . The crosslinked sulfur of the type readily reacts with structure represented by the above -mentioned compositional water to generate hydrogen sulfide. For example , when the formula Liz _ PS6 - Ha ( Ha represents Cl or Br, x is prefer proportion of lithium sulfide (Li2S ) in all the raw materials ably 0 . 2 to 1 . 8 ) is preferably a cubic crystal, and in X - ray is small , a crosslinked sulfur is readily formed . “ Not sub diffractometry using a CuKa ray, the crystal structure gives stantially containing a crosslinked sulfur " can be confirmed peaks appearing mainly at 20 = 15 . 5°, 18 .0° , 25 .0° , 30 .0° , through Raman spectrometry . For example , in the case of a 31. 4° , 45 . 3° , 47 . 0° , and 52 .0° . Li2S - P2Sz -based sulfide solid electrolyte , in general, a [ 0073] These peak positions may vary within a range of peak of a structure S P - S - PS , appears at 402 cm - ? . + 0 . 50 Consequently , it is desirable that the peak is not detected . In 10074 ] The crystal structure of the crystalline solid elec addition , a peak of a structure PS4 - generally appears at 417 trolyte includes one represented by a compositional formula cm - 7 . In the present invention , preferably , the intensity 1402 Li Si P S Ha, (Ha includes any one or more of Br, C1, I and at 402 cm - l is smaller than the intensity 1417 at 417 cm . F , 2 . 4 < ( x - y )/ ( y + z ) < 3 . 3 ) and having an S content of 55 to More specifically , for example , the intensity 1402 is prefer 73 % by mass , an Si content of 2 to 11 % by mass and an Ha a bly 70 % or less of the intensity 1417 , more preferably 50 % element content of 0 .02 % by mass or more , more preferably or less , even more preferably 35 % or less . US 2018 /0170756 A1 Jun . 21, 2018

[0079 ] Examples of the shape of the crystalline solid electrolyte of the present invention that includes reacting electrolyte include granules, though not specifically limited two or more kinds of solid raw materials. The structure and thereto . The mean particle size (D5o ) of the granular crys the use conditions for the multi - axial kneading machine of talline solid electrolyte is , for example , preferably within a the present invention are the same as those described here range of 0 . 1 um to 50 um . The mean particle size (D50 ) inabove in the section of the solid electrolyte production means a particle size to reach 50 % of all the particles as method of the present invention . sequentially integrated from the particles having a smallest particle size on the particle size distribution cumulative EXAMPLES curve drawn with particles, and the volumetric distribution can be measured , for example , using a laser diffraction / [0087 ] Next , the present invention is described specifically scattering particle size distribution measuring device . with reference to Examples, but the present invention is not [0080 ] The crystalline solid electrolyte obtained by the whatsoever restricted by these Examples . production method of the present invention has a high ion conductivity and excellent battery performance , and are (Measurement of Ion Conductivity ( o ) ) therefore favorably used in batteries . The solid electrolyte [0088 ] The solid electrolytes obtained in Examples and using a lithium element as the conductive species is espe Comparative Examples were respectively shaped into a form cially favorable . The solid electrolyte obtained according to having a cross section of 10 mmo ( cross - sectional area the production method of the present invention may be used S = 0 . 785 cm ? ) and a height ( L ) of 0 . 1 to 0 . 3 cm , thereby in a positive electrode layer or a negative electrode layer , or preparing sample pieces . From the top and the bottom of the may also be used in an electrolyte layer. Each layer may be each sample piece , electrode terminals were taken , and the produced according to a known method . ion conductivity was measured according to an alternate [0081 ] The above -mentioned battery preferably uses a current impedance method ( frequency range : 5 MHz to 0 . 5 collector in addition to the positive electrode layer, the Hz, amplitude : 10 mV) to give a Cole - Cole plot . In the electrolyte layer and the negative electrode layer, and the vicinity of the right end of the arc observed in the high collector may be any known one . For example , a layer frequency side region , a real number part Z ' ( 22 ) at the point formed by coating Au , Pt, A1, Ti, Cu or the like capable of at which - Z " ( 2 ) is the smallest was referred to as a bulk reacting with the above- mentioned solid electrolyte , with Au resistance R ( 2 ) of the electrolyte , and according to the or the like may be used . following equation , the ion conductivity 6 (S / cm ) was calculated . [Production Method for Inorganic Material ] R = P ( L / S ) [0082 ] The production method for an inorganic material of the present invention includes reacting two or more kinds of o = 1 / p solid raw materials using a multi - axial kneading machine to [0089 ] In Examples , the lead distance was about 60 cm . give a crystalline inorganic material. Not specifically lim ited , the solid raw materials may be any ones that react with (Measurement of Purity of Lithium Sulfide ) each other to give a crystalline inorganic material , and 10090 ] The purity of lithium sulfide was measured by examples thereof include a zinc sulfide- type light emitting analysis with hydrochloric acid titration and silver nitrate material, a molybdenum sulfide - type and vanadium alloy titration . Specifically , the lithium sulfide powder obtained in type thermoelectric conversion materials , etc . Production Example was metered in a glove box (dew point: [0083 ] As the multi- axial kneading machine, the same one about - 100° C . , nitrogen atmosphere ) , dissolved in water, as that used in the production method for the solid electro measured using a potentiometric titrator (“ COM - 980 (model lyte of the present invention may be employed . number ) ” , manufactured by Hiranuma Sangyo Co. , Ltd . ) , [ 0084 ] The temperature at the reaction of the solid raw and calculated . materials is preferably not lower than the crystallization temperature of the crystal structure that the crystalline solid Production Example : Synthesis of Lithium Sulfide electrolyte obtained by the reaction of the solid raw mate (Li2S ) rials has , and the other reaction conditions are the same as those in the above -mentioned solid electrolyte production [ 0091 ] 200 g of lithium hydroxide (LiOH ) anhydride method , and by heat - treating the resultant crystalline inor (manufactured by The Honjo Chemical Corporation ) dried ganic material, the crystallinity thereof can be further in a nitrogen flow current was put into a 500 -ml separable improved like in the above -mentioned solid electrolyte flask equipped with a stirrer . This was heated in a nitrogen production method . flow current, the internal temperature was kept at 200° C . , [0085 ] According to the production method for an inor and nitrogen was changed to hydrogen sulfide (manufac ganic material of the present invention , two or more kinds of tured by Sumitomo Seika Chemicals Co . , Ltd . ) and supplied solid raw materials may be reacted using a generalized at a flow rate of 500 mL /min to promote the reaction of machine such as a multi - axial kneading machine to produce lithium hydroxide and hydrogen sulfide . Water to form with a large variety of inorganic materials in a simplified manner the procedure of the reaction was condensed with a con denser and recovered . At the time when the reaction was with excellent productivity and mass - productivity . carried out for 6 hours ( 6 hours after hydrogen sulfide introduction ) , 144 mL of water was recovered . The reaction [Multi - Axial Kneading Machine ] was further continued for 3 hours , but there occurred no [ 0086 ] The multi - axial kneading machine of the present water generation . A powdery reaction product was recov invention is used for production of a crystalline solid elec - ered , and the purity thereof was measured according to the trolyte according to the production method for a solid above -mentioned method , and the purity was 98 .5 % . In US 2018 /0170756 A1 Jun . 21, 2018 powdery X - ray diffractometry (XRD ) , the product gave a solid electrolyte obtained in each Example has. In addition , peak pattern peculiar to lithium sulfide (Li2S ) . it has also been confirmed that according to the production method of the present invention using a generalized machine Example 1 such as a multi -axial kneading machine , a crystalline solid [ 0092] In a glove box filled with nitrogen , a feeder (“ Mi electrolyte can be obtained in a simplified manner with cron Feeder (product name) ” , manufactured by Aishin Nano excellent productivity . Technologies Co . , Ltd . ), and a biaxial kneading machine INDUSTRIAL APPLICABILITY ( “ KRC Junior (product name ) ” , paddle diameter : 08 mm , manufactured by Kurimoto , Ltd . ) were arranged . A mixture [ 0097 ] According to the present invention , a crystalline of 3 .828 g of lithium sulfide ( Li , S ) obtained in Production solid electrolyte can be obtained with excellent productivity . Example and 6 . 172 g of diphosphorus pentasulfide (P2S3 ) The crystalline solid electrolyte has a high ion conductivity (Li , S :P2S3 = 75 :25 (molar ratio )) as solid raw materials was and has excellent battery performance and is therefore fed to the supply port of the kneading machine from the favorably used in batteries. Using a lithium element as the feeder at a constant rate , and began to be kneaded at a mean conductive species is especially preferred . motor torque of 0 . 8 Nm ( load ratio : 60 % and at a screw REFERENCE SIGNS LIST revolution number of 150 rpm . In about 30 minutes after the [0098 ] 1 Casing solid raw materials were supplied from the supply port, a [0099 ] 2 Supply Port reaction product was discharged out from the discharge port . [0100 ] 3 Discharge Port The discharged reaction product was again returned back to 10101] 4a , 4b Rotary Shaft the feeder and the kneading operation was repeated . (0102 ] 5a , 5b Paddle [0093 ] The resultant reaction product was analyzed [0103 ] 6a , 6b Screw through powdery X -ray diffractometry (XRD ) , and as shown [0104 ] 7a , 76 Reverse Screw in the X - ray analysis spectrum thereof in FIG . 3 , a crystal 1 . A method for producing a solid electrolyte , comprising lization peak belonging to the crystal structure of BLizPS4 reacting two or more kinds of solid raw materials using a was detected , and the ion conductivity of the reaction multi- axial kneading machine to give a crystalline solid product measured according to the above -mentioned method electrolyte . was 2 . 0x10 - 4 S /cm , which confirmed that a crystalline solid 2 . The method for producing a solid electrolyte according electrolyte having a crystal structure was obtained . The to claim 1 , wherein the reaction is carried out in a solid state . temperature at the outer surface of the casing of the kneading 3 . The method for producing a solid electrolyte according machine during kneading was at most 90° C . to claim 1 , wherein the solid raw materials contain a lithium element, a phosphorus element and a sulfur element. Example 2 4 . The method for producing a solid electrolyte according [0094 ] A reaction product was obtained in the sameman to claim 3 , wherein the solid raw materials contain at least ner as in Example 1 , except that , in Example 1 , the solid raw one of a lithium compound and a lithium metal elementary materials were a mixture of 2 . 78 g of lithium sulfide (Li2S ), substance , and at least one of a phosphorus compound and 4 . 435 g of diphosphorus pentasulfide (PS2 ) , 1 . 425 g of a phosphorus elementary substance . lithium iodide (Lil ) , and 1 . 385 g of lithium bromide (LiBr ) 5 . The method for producing a solid electrolyte according ( Li , S : P . S . :Lil : LiBr = 56 .25 : 18 .75 : 10 : 15 (molar ratio ) ). to claim 3 , wherein the solid raw materials contain lithium [0095 ] The resultant reaction product was analyzed sulfide and phosphorus sulfide. through powdery X - ray diffractometry ( XRD ) , and as shown 6 . The method for producing a solid electrolyte according in the X - ray analysis spectrum thereof in FIG . 4 , a crystal to claim 3 , wherein the solid raw materials further contain a lization peak belonging to Lid - Ge P . S - based thio -LISI halogen element. CON Region II -type crystal structure was detected . The 7 . The method for producing a solid electrolyte according resultant reaction product was heat- treated at 200° C . for 3 to claim 6 , wherein the halogen element is at least one of hours , and the ion conductivity of the resultant product bromine and iodine . measured according to the above - mentioned method was 8 . The method for producing a solid electrolyte according 3 .0x10 – 3 S / cm , which confirmed that the product is a crys to claim 6 , wherein the solid raw materials contain at least talline solid electrolyte . The temperature at the outer surface one of lithium bromide and lithium iodide . of the casing of the kneading machine during kneading was 9 . A method for producing an inorganic material , com at most 80° C . prising reacting two or more kinds of solid raw materials [ 0096 ] The solid electrolytes obtained in Examples all using a multi- axial kneading machine to give a crystalline gave a crystallization peak belonging to a crystal structure , inorganic material . which confirmed that these solid electrolytes have a crystal 10 . A multi -axial kneading machine for use in production structure . From this , it is considered that the reaction tem of a crystalline solid electrolyte , the production comprising perature would be a temperature not lower than the crystal reacting two or more kinds of solid raw materials . lization temperature ( Tc ) of the crystal structure that the * * * * *