JO and INFIT are nol reaponsiile for any damagescaused by thease atinistarmiistion.
`
`
`
`4. TAs Soames See tae ansisis hy comnaulerGa the iaeetehoss mayned cofhect Ihe orginal arscivady.
`
`
`Fublicaton Number
`
`JPSOROS TS164
`
`
`
`Bibliograahy
`
`M9) [Publication country] JR
`(is) [hind of official gazetiel A
`fF) fPublication number] BOTS 1448
`
`(43) [Date of puldication of appli¢ation) 201420
`
`(Od) [Tite of the invention] COMPOSITE MATERIAL,METHOD FOR PRODUCING THE
`SAME. GATHODE ACTIVE MATERIAL
`OATHGQGE AND NONAQUEOUS
`
`ELECTROLYTE SECONDARY BATTERY
`
`61) [international Patent Classification]
`GOB S32
`{2008.07}
`HOIM 4/58
`(2610.07)
`HOIM 4.36
`{2006.01}
`
`(Fil
`
`COI S382
`
`HOIM 4768
`
`HOIM 4/36
`
`G
`
`(21) [Application number] 20T2198128
`{22}[Filing date] 2o12asiG
`Tt} fApolicant]
`iNamel TOYOTA INDUSTRIES CORP
`
`oohes NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL & TECHNOLOGY
`2} finventort
`Hh
`“ull ame] KOJIMA AKIRA
`Ful§ aamel KOJIMA TOSHIRATSL
`
`wrrey ysinre"ap
`Ful name) SAKAI TETSUD
`(Full name] RAWASUMI KAZUNITO
`
`

`

`Ful name] NAVA JUNICHI
`
`‘Theme code(reference
`
`#5072
`
`SHOSG
`
`iF-tenn (reference) |
`AGOSBAGS
`
`SGTSBASS
`
`4QO7SBA38
`
`SGOTSBASO
`
`AGOTSBASS
`
`4S07SBA83we
`
`SEOFSUBGO
`
`SMOSGAAGS
`
`

`

`SHOSOEADS
`
`NOSUFATY
`
`SHOSOFAIS
`
`SHOSOGADZ
`
`5
`
`SS90H
`
`4cSot
`
`
`
`SHOSOHALeywe
`
`RHOSONALS
`
`
`Abstract
`
`{87} Overview!
`that can enhance
`PROBLEM TO SE SOLVED: Te provide a composite material
`discharge capacity of a battery when using he same as acathode active material, te
`provide @ method for praghining te composite material and fo provide a cathodeactive
`material, a cathode and g nonagueous electrolyte secandary Gattery.
`SOLUTION: The commaaits enaterial has @ secondary particia farmed by aggregating 3
`Oluralty Of primary particles. The primary paricie 6 Composed of @ Sillcale sore pat
`COmionsing € Hihtuin silicate comm@ound including Hihthuch (Li, sticon (Si) and oxygen 1)
`
`and a carbon cealing pert comprising 3 carbon maternal and coating he surfaceof ihe
`adicale core part.
`
`

`

`
`Claim
`
`wore,
`
`Patent Claims]
`
`{Chant ¥]
`This composte matertal has 2 primary pariicies obtained by aggregating a sluraity of
`orimary Sarticies,
`The composite maternal is characterized in that the arimary panicles comprise 4 silicate
`core goron made cf a Nhien aiicats cameaund containing Nha (4), sticen (S4and
`oxygen (O}, and a carbon coating portion made of 8 carbon matenal and covering the
`surface of he silicate core portion.
`
`Chain 2}
`
`Fee composite material according fo cisim (1. wherein the Whom. siicate-based
`
`
`cenmpound is represented by ihe general formuda Litedyi i) +zhibew
`
`iM. is 7 or more
`
`selected from Ps, and Co, and OG 2b<y<0.8 Dez<0 2 and O aw <i 2)
`
`‘Ielaien 3}
`The composite material according te claim 1 or S, wherein an average dlameterof the
`a
`aiicaale cave portian is 48. omor more and tS8.nm or jess:
`
`faim 4]
`The composi maternal according fo any one of chime 1 to 3, whereit an average
`Meckness af ihe carbon coating partionis 2 Am or more and20 am ar less.
`iCiain S]
`
`The composite material according fo any one of claims 1 to 4, whergin the primary
`panicle diameter afthe. orimary particles 9 50 nmof ions and 200 nn or less,
`
`iClain 8]
`The composite material according to ary oneof claivis 7 fo 6, wherein ihe secondary
`gerticle diameter of the 2 particle is from 100 fm to 10 pom inclusive.2.
`
`Cian F]
`The compose material according to any oneof daims fT to 6, wherein pores areformed
`in the 2 particles.
`Slain 8]
`The carmposita material of claim 7. wherein the average diamwter of the pores is less
`
`than or squalte 20 nes.
`SChaim 8}
`The composite matenal accurdingto any ane of claims ( fy 8, wherein a mas rate of
`
`ihe carbon material is 8% by mass or more ard 30%by mass or less wherthe taal of
`
`the contposite material ig 1005s by mass,
`
`

`

`:i
`
`faite: TO]
`moh
`The method for manufacturing a composite matenal coninises @ 2 gamerparice
`formed by aggregating a plurality of primary particles, and a carbon coating portion
`
`composed of a carn material and covering 4 surface of ihe sing core portion, wherein
`the oriniary paricls comprises. lfhiun silicate compound centaining When(Li) siicon
`(EH and oxygen (OD).
`
`
`An energy inipariing step of appiingmechanical energy in ihe pres
`arigeOf e solvent ta
`3 fay material of 8 compound as a naw material of the [thus siisate-based compound
`and a carbon nawmaterial a6-arawmaterial of ihe carbon material to obigin a mined haw
`
`material consisting of ihe cawmaterial of the compound and the carbon raw material :
`
`A Granuating sieo of dating the solvent and granulating ihe mined raw matenal by soray-
`
`drying ihe mixed raw material io which the mechanical energyis applied in the presence
`
`of ihe solvent;
`
`A mathodfor Groducing @ composite material, comprising a heat reatnent sieo of heat-
`ireating the granulated mixed raw material,
`
`Aumethod for producing @ conyansite maternal accoriing in claim 10, wherein apraydrying
`of the mived raw material i performed in order te spray airy the mbesct rsev ntatenal js
`ihe granuigken step.
`iGlalm is]
`
`This athod of manuiactuning & composite matenal according to daimTor dt wherein
`
`the heat ireatment performed in ihe heal freaiment step is perfonned st 650 °C. ar more
`
`and 100 °C. ar les
`
`Clainy 13}
`
`The heat ineahnent of claim 10, wherein the heat treaiment is performed in & range of
`
`OS hours to 18 hours, 12
`
`A mathod of manufacturing a composite malerial according to any one of the above
`
`lain id]
`
`The method of manufaoluring 8 campasite material accurding ta any one of claives 10%
`
`TSavherain fhe compound paw material includes a ithim pawmaterial having a ihm
`source, a metal nw material containing a fansition metal source composed of 1 or more
`kinds selected from Fe, and Co, ard a silicon paw aterial having & SHicor source
`
`(Chair 15]
`Thee avethodfor producing a camposte material accerdingto any ane af clairas 1Q to 44,
`
`

`

`whersin IN& compound rawmaterial includes @ ssaringly soluble component which
`Hardly soluble in the salvent,
`iGiait 16]
`
`‘Fhe nvethod of manufacturing a composite maternal according to claim 14. or 15, wherein
`{he ENicon raw material is SiO 2.
`
`Chain 17}
`‘Fre method of sigeiaciunng @ composite migterial according tO-any ane of claims 14 te
`16, wherein 4 particle diameter ofthe silicon raw material is 50 neor more and SOG nm
`
`or fess.
`
`iGhaint 18]
`
`The method for praducing @ cormposte material according toany ornof cigs Tite TY,
`
`wherein the carbon raw materials dextrin.
`
`(Claim 19}
`
`‘The method for producing a composite material accordingto any one of claims 10 fo 18,
`wherein, when agalying the mechanical energy § the compound naw material and the
`carbon fav material oiling is performed,
`iclaim 20)
`& posiive electrodeactive subsiance compnsing & composite maienal according to any
`one of cians 1 fo G or 8 composite mutenal prodeced Dy a process for producing a
`composite material accerding to any aneof claims 1940.79.
`
`[Cigin 21}
`
`A positive slectrade coninrising & postive siectradeactive subsianceaccording ix clan
`20.
`
`Risin 22}
`Anonaqueous electrolyte Secondary battery comprising: 6 positive slectraceaccording
`fo Gaim21 A negative clecirade | and an slediralyte. 2.
`
`Description
`
`(Oetailed desecration ofihe invention)
`‘Technical field)
`COT}
`
`The present invention relates bos camposile material which can be peed as a goes
`electradeactive subshance, a method of manufacturing the Same, a doesiiive electrade
`active substance, a oositive elgcirads, and a nonaquequa sleciohuc secondary baliery
`
`(Background of the invention!
`
`

`

`(OZ]
`The nonaqueous slectroiyie secondary battery is widely used as @ power supolyof
`portable electronic equipment As ihe positive electradeactive substance, & commasite
`
`oxide such ag LiOoGs.LIMNSO4 is mainly used. However, when fessecomynosifeanides
`are fully charged, oxygen tendsto be desorbed at around 150° C., and thus the desorbed
`oxygen tends fo cause an oxidation exothennic reaction ofthe nonaqueous alectrolyte.
`AbOui these composite guides, F conductive carbonis added when praducing @ shuny
`since electron cenductvity (conductivity) &- comparatively high,
`the electrode for
`somaquecus slecioivte secomfary batteries which is excellent
`in a charging and
`chacherging charecteriaic canbe obtained.
`
`(003)
`
`in recent years, 8 phcsphaie material LAMPO. sub. 4 fat least } types selected from
`
`among M=Fehin,Gojand @ silleate material Li sum. 2 MGI. sub. 4(atleast one selected
`
`from the group consisting of M=Ps,Mn.Co} have attracted attention as & positive
`wincivods active substance in viewof high safety are resource amcuniaf the. 7. However,
`these composite okies haveiow electrical conductivity and are almost atthe ingulator
`level. Therefore, & is. necessary to add a large amount of carbon material to these
`
`composife oxkles to dnpart conductivity.
`O00)
`However, witht 4 lagje amount of carbon material is added to te commagite oxide, the
`
`energy density of ihe postive slectode active Substanes iS how.
`
`Thereis 8 sratlern of being lowered,
`
`(OINSS}
`Fhe aiectrode for nonaqueous e@lactvolyts secondary batteries which is excellant in a
`charging ard discharging characteristic cannot be obtained only by adding conductive
`
`carbon inte positiveachvemaiodal matenal, wherproducing & Gury,
`
`fO008)
`in order fo mix a carbon material with a composite oxide, conventionally, ft has Geen
`proposed io perfont spray drying treatment such a8 spray anying reatment. Far example,
`as disiosed in Patent Document 1, a comeosite oxide comprising a LHCOD? LIMN2Oeis
`
`grovided, His disclosed that affer mvxing a carbon pawder jconduchve aid), a binder, and
`@ solvent by @ bal ma a Spray drying process is performed onthe midture, and a solvent
`is dried to form a conipasite maternal in which @ cormigesie oxide ia held argued the
`
`carbon peawier, Patent Qocuments 2 and 3 disclosethet a 2 particle camprising slican
`and Ketier: Diack is formed by @ spray drying methedt, and then @ chemical vagor
`
`

`

`deposition method (VD) is gerfonned using imluene gs a carian source to coat a
`compasite particle af350 "0. with carbon.
`{OOF}
`
`Patent Docuanenis 4 and 8 disclose that particles are formed by oerfoning & soray
`dying process of active material particles Such a8 Si and Sn, 3 carbon material, and a
`binder material, and then the particles are stived andl aised by rotation af a rotating
`blade lo pragara a paste, arid than the paste is apolied ta a currant collector,
`XN
`Patent Document 6,7 discloses obtaining 2 ithhummanganese composite oxidebysoray
`drying, Patent Document 6 discloses that 8 spray drying process is performed wien 3
`
`conductive metenal made of cetiene bieck is dried. in addition, Patent Document 9
`disclosesthat @ carbon material mixed with an glectrode active material is preferably
`teeth
`(Priorart reference
`Patent document]
`(O009]
`{Patent decument TUR S003. 1 PSPPPA
`{Patent document SP 2008-30
`~SOSSSSA
`<
`TaSaess
`
`Patent document SP 2G05-
`(Patent document 4LiP Zone.
`
`eeannla
`
`,a
`
`Oa04
`
`iSpe
`
`y ix
`
`FOOTE]
`The present invention has been extensively mseerched in order to manufacture a
`composite material which can be used as 8 postive electrodeactive subsignce having
`& high discharge capacily by a method diferent frani tha method disclosed in Patent
`
`Deacuments J tag
`
`wrt wae.
`(0014)
`in view of guch circumstances,is an oblect of fhe present invention to provide a
`
`composite material which can increase a discharge capacity of s battery when used as
`
`@ positive eiectradeactive substance, 8 method of manufaciuingthe composite maternal,
`
`(Patent document SLIP 2010-4 14
`(Patent document GUP 2006-93 7
`S24
`wo
`78
`TSA
`y
`arte A
`f
`
`boweEd Da
`
`ao
`
`
`
`Patent document ine
`Fatent dacurent auP-22
`Surarmary of tre invention!.
`Problern te be saived by the invention]
`
`

`

`a positive siectrods active substanos, & postive electing, and a nonaqueous secondary
`battery 2.
`iMeans for solving the probleny]
`
`ee=
`primarypartiesobkainadby Sggregatngaa pluraltyof primaryparticles.
`
`THe primary garticies comgise @ siicale core portion siade of a Whur siicate
`
`commound containing iitigm (0), silean (Sh and oxypen (0), and a carbon coating
`
`8
`sarfion made of 3 carbon material and covering the surface ofthe silicate core portion.
`
`iS) A method for producing @ composite matenal according te ihe present invention,
`wherean iNG prhriery panicles Nave secondary aanicies obtained by aggregating 8
`luraity of primary particles, and ihe primary pariicies are oblained by adgragaiina 4
`
`muralty of primary particles . are ¢ The method for preducing a composite material
`SONyyises a silitele core par comprising MMisilicate baseet cemnpound containing
`Rihlum (LH, silicon (3) and oxygen (O) and a carboncoating part consisting of a carbon
`maternal andcovering the surface of {he Silfoate core part.
`
`An energy inpariing step of apphing mechanical energy in ihe presence of a sohvent te
`a raw material of a compound a8 a raw material of Ihe ithtum Siisate-besad compound
`and 3 Carbon raw material a6 a rawmaterial of thecarhan material © obfain 4 mixed raw
`
`mateal consisting of the raw material af the compaund and the carbon raw material :
`
`A granulating sige of drying the solvent and granuisiingihe mixed rawiigienal by soray-
`drying the otined rawmaterial io which the mechanical energy is applied in the presence
`
`of the solvent <
`The heat treaiment sracess which heattreats to the aforementioned mixedraw material
`by which granulation wes carriad out [ aforementioned | is performed.
`
`i3} A postive electrode active substance according to fhe present
`
`invention &
`
`charsetariged i that Ht is made of the comipesiie material or a composite mataial
`manufactured by ihe manufacturing mathad of ihe composite maternal.
`(4) The positive electrode of the present invention is characterized in hat f hes the
`
`abave-mentioned gostdlectrodeachive subshance.
`eo
`&&(S) The nonaqueous alectolyte secondarybattery of the presen invention osprovided
`withHe aforementioned positive slectrode, an srode, ard an slactroht
`
`fees ofthe hrverntion!
`
`wm,ae
`
`icAceorcing to ihe composite material of fhe present invention, @ guralty of primary
`
`

`

`particies camposed of & silicate core portion made of § Nhium siicate compound anda
`carban ceating portion made of 8 carbon material and covering the surface of the silicate
`core portion are agqregatadand comisned. Thus, ihe composife maternal car inmrease
`
`the dischame agoacity of ihe battery, Since the above-mentioned composite matarist is
`used for he postive active civledal, postive electrode, and nonaqueous slectrolve
`secandarybattery of the gresent invention, their serving capacity i high.
`{Brief Description of the Drawings]
`OOS]
`Fig. THUGS an explanatory view of a heal siomiser.
`(Fig. SIFIG. 3 is an SEM (scanning electron Teroscope) ohotagraoh of a mixed raw
`
`material after a Spray drying process of Sanipie 1 and before theheal featment,in which
`
`ihe magnifications of ie upper, middle, and lower phofagqranhs are 3.000. 5,900. and
`
`YO.000, respectively:
`
`Fg. SIFIG. 4 is an SEM photegraph of a cermposite maternal after heat reaiment of
`Sampist.
`(Fig. 4]F IG. 1 is an SEM cross-sectional photograph of secandary particies of Sample 2,
`and rragnification magnilications of the upper and lower photographsare 20,000 = and
`SOAUNN x, pespectheshy :.
`Pig. SIFIG. 3 is an SEM cross-sectional photograph of @ composite material of
`CaunparaiveSaye 1.
`
`(Fig. GIF ES. 4 shows changing and discharging curves of @ battery using @ composite
`matenal of Sample 1
`
`Fig. FIFIG. 4 shewe charging ard discharging curves of 4 battery using 8 compose
`
`maternal af Comparative Sample 7.
`Fig. SIG. 4 is a diagram showing an XRD analysis result of Sample 2.5.
`(Fig. SIPIG. 4. 8 a qraphshowing KRD analysisreauits of Samples T and 4
`(Fig. TOURING. 4 is3 granh showing ARO analysis resulls of Sammies 14to ¢ te
`
`(Fig. (TIFHS. 3 is an SEM shotographaf a compoate meterial of Sarinle G7 wherein
`ihe upperstage shows Sample§ and the lowerstage shaws Sample ¢
`iFig. TS]IFNG. 3 is
`an SEM photograph of a composite material of Sample $5, wherein
`ihe unger Mage shows Samals § ane the lower stage shows Gample §.
`
`(Pig. SSF. Sis ary SEMcross-sectional photogragh of a 2 particle of Sample 8, and
`ihe magnification of the ugger stage and the lower stage is 20.000 tnes aad $0,000
`{hnes, Pehoeciively |.
`
`Fig. T4]RG. 438 3 charge-dischargecurve of & battery using @ composite material of
`
`Saris Of, wherein the uoser slage shows Semiole G and ihe lower slage shows
`
`

`

`Sample *
`(Fig. 188iG. 4 Is a charge-discharge curve of a battery using @ composite material of
`
`Sample 3,9. wherein the ugner slage shows Sample & and the lower stage show
`Sample 9.
`(Fy. 1GiR iS @ conceciual explanatory view of the composite material of the present
`ra
`AVENE,
`
`(Madefor carrying out the inventions
`POOST
`
`A composite maternal, 9 method for manufacturing the same, a positive electrode active
`
`substance, & positive electrode, and & nanaqueaus secondary belfery according fo an
`
`embednniant of ihe aresent invention will be descrited in detal with reference ta FNS. 2.
`
`
`{NS}
`
`(Canposile matte)
`The composite material of the present invention has 2 primayy particles obtained by
`aggregating plurality of primary saricles. The onmeryparticles comprise& silicate core
`made of a INhium. slicate-based compound arc a carbon coating oeie of a carbon
`
`material anc covering the surface of tive silleate particles,
`pores,
`OO]
`al
`he atigate core portion in. ihe primary Serticies has @ relatively small average dianmter
`
`aod is finely dispersed in ihe 2 panicles. The siicale core portion is made of @ Hiiiumn
`
`giicate-hased compound, and © preferably a single phase wihless inpunties. When s
`composite mabsriatie used asa positive electrode acive substance of a battery, a silicate
`core. partion performs a battery reaction for staring and retegsing Mihm ions. Then, &
`surfsce of he sNicate care portion is covered with a carbon coating layer made of a
`cardon material, The carbar coating layer is conductive (electonically conductive) and
`
`increasesthe conductiwiy between ihe silicate core porions, Therefore, a batteryusing
`a composite malefal as a postive siectode active substance has excellant charcne-
`discharge characteristics.
`fOO1 8}
`
`
`The Shum slicate-based compound constituting theelicate core portion includes iRhium
`
`{LA e8icon (Sh art axyeen (O). in the [ahaen siicate-based compound, Lit Mas 4 it
`i Y oF midre Selected from Fe,, and Co} is @ basic composition, bul some of Li, M. and
`Si ary be substituted with other elements, Wher tis substituted with another element,
`
`{is preferably performed within a range aot adversely affecting the capacity, Aisa
`wicivdedie a fidign) auicate-based compoaurt! having a comission slightly shifted fram
`
`

`

`ihe shove composition formula due to inevitable lose of LEM> Shor O and anidation- of
`ihe commaund. A preferred ithisn sWieste compound has & basic composition of a
`general formula Li+eyhiergigdsw 6is 1 or mor selected fram Fe, and Ca, and
`O.SS<ys0.8,Cero.2 and & sw <7 25.
`0073}
`Preferably, the Midian siicate-based compound ia monocinic and belongste ihe space
`group Pot fn.
`POLO
`Vile ithium siicate-hased compounds partiopate in oell reactiona, many of them do sot
`paricinsis in hettery seactions. Therefore, it iS preferabie that ne silicate core portion is
`
`composed of a single phase composed of a ithiut silicate scompourndl. in other words,
`whe siege core gortion 6 composed of a Single Base composed of a Num silicate
`
`compound, and oreferably oondains ne iypurties.
`
`fOG2 T}
`\Whenthe total of he composite material is 700%by mass, the massratio of thehin
`slicate-based compound constituting the silicate core portion is prefwrably from 80%by
`mass to BS6 by niass, and more preferably from 3558 by mass to BS40 by mass. When
`the weight catio of the iNhiurn silicate compound ts foo small, ihere is a possibilty that a
`portion of ihe camooads material conidbutes to &battery reaction and @ battery capacity
`decreases, When the weight rane of the fithiumsilicate campound is exceasively large,
`
`there iS a PoSsainity that the carian cogting portion becomes relatively small and the
`
`CTUciny of INS COMPGSIS MaTial COCMeasss.
`(O22}
`The silicate core portion hes, for exgmoele, a fist shage and @ spherical shape. 2 is
`oroferable that 4 plurality of the silicate care portions are arrangedparallel ia each other
`aot
`ae
`in
`the 2 partcies. Thus. there is an effect that pores: are generated behween the orimary
`
`ganicies andihe diqued setention of ihe sleciralytic Solktion &impmeyed,
`
`Preferably, he average diameter of the silicate core portion is 48 nor more and 196
`nm or lass. For eveample, fis calculated by averaging the dlamisters of a pluralityof
`sticate cere portions observed from an SEM image of a composite material i the
`average cametey of fhe siitate core portion is toa smell, the primary particles coated
`wilh {he carbon coating isyer tend to scelter, which may make R dificuilte Randia, When
`
`ite the inside of ihe siitate core portion is delayed.
`
`

`

`.
`There is & gossibilityhat the rate characteristine and the discharge cananity decrsass.
`ned}
`The carbon coating portion is comipased of ¢ carban nigterial icarbon particles}, Carbon
`
`articles enhancetie conductivity of fhe commosiie material.The carbon panicles cover
`@ portion or the entire surface of the sucface of the silicate core ponion. The carbon
`mistefal consitiuding the carer coating layer is mainy a metenal having carbon. The
`
`carbon matenal
`ig meade of amorphous carbon or the Nke fiymed by thermal
`decamponition of a carbon matenal such as dextrin.
`poo2}
`When the total of the composite material is 100% by mass, he mass ratio of the carbon
`migterial 1s orefersily fram Sos byfiaes fo SOS byriees, and more oraferaily framOs
`by mass to 15%by migss. Whenthe weight ratio of ihe carson material is igo small, there
`S a possibiltythat the conductivity of fhe composite material decreases, When the mass
`ratie of the carbon material is excessivelylarge, the mass raiioofthe silicate core portion
`iS Tatively decreased, and tha portion of the composiie misterial contrasting to the
`batiery reaction is reduced, which may reduce the battery capacity of he composite
`material,
`
`(OO26}
`The average thicknessof te carbon coaling portion is preferably from ¢ nmfo 20 nn,
`ancl more preferably from 3 am to (0 ant. The average thickness of the carbon coating
`gortion refers fo an average value of the thickness af ine carbon oeating layer ccated
`
`wath IheOritiary parities, and is caltuisied by, fie example, observation of fransriesion
`siectran microscage(TEA) of the primary partiches, \When theaverage hickness of the
`
`carhert coating portion is foo smell, there is @ soasibiity that ihe conducthty is lowered
`without covering the entire surface of the silicate core portion. When the average
`Glameter af the carbon coating partion is @icessively lange, there is a pOSSIANtythat a
`
`relatively small amount of the siicete core portion contributes to the Rattery reaction and
`
`the batlery cagacity decrsases,
`{OOFI
`Hy coating the surface of ihe siicaie core sorton with @ carbon coating portion, oimary
`saricles are fonned. The primary particle diameter of ihe onmary particles is preferably
`SO armar more and 200 nivportess. The prenary particle diameter of the primary particles
`refers to an average diameter of ihe otimary parlicies, and is calculated by, for example,
`averaging the diameters of a plurality of primary particles observed from an SEMimage.
`of the composite material Wher the primaryparitte diameter af the primary particles is
`too eral, vere ig a possiity that ihe orimary particles tend to scatter and became
`
`

`

`dsficull io hartdie. if ihe orimarypartige diameter of the primaryparticles is excessively
`‘args, ihe Garlact area behween the primary Garticies may decrease, and the battery
`capacity may decrease.
`
`{OO38}
`The secondary partice dianmieier of the 2 paricie is oreferably fron: 100 nei fo TS gm,
`and more preferably from 2 om to $ p mand uvther preferably from$00 nnvite p mA
`
`secondary paricie diameter of gS partie fefers fo an average dlanveler af a2particte
`and is calculated by aversging & Miameter of & pluraity af 2 particles afserved fram an
`SEMimageof a composite material, for axanipie, by averagingthe 2 particle diameter.
`if the secondary particle diameter of the 2 particle is foo arma’, the @ particle tends to
`
`scatter, and & is dificull to handle the 2 paricie. When the < particle dlameter s
`pkceusivelylarge, when the2 panicles gre used 83 8 nosiive electrode aclive aubstance,
`ihe permeabiNyof ihe electrolyte to ihe inside of he 2 paricies decreases, and ihe
`
`reactivity of the battery reaction inside the 2 particies|may decrease,
`fOOL9}
`Fores may beignnedInthe2particies. The pores are gans betveen the orimaryoariicies
`present in theinterlar of ihe 2 particies, The pores are surrownied by 4. carban canting
`
`and {ara silicate core which consiiutes the primary particies. This gore serves as an
`son canduction path through which ihiumjones fos, and thus the ion conductivity of the
`composite material becomes good. in addition, an electratyte is held in Ihe pores, and a
`
`eal yeaction insite the 2 particle tends to proceed,
`
`fOO30}
`Fhe average clameterof the cores formed in the 2 particles is prefenabiy 20 nn or less,
`and snore preferably 15 nv or less, The average diameter of pores refers ip an average
`value of each pore and is calculated by a gas adsorption methed.
`if the sanes are
`
`excessively large.g portion which does fot cartribule toine battery reaction becomes
`large, and the discharge capacity may decrease.
`
`O04]
`Ssiow HO.m2/gis goad, and aisa th
`is [ytiore than 20-mniig | 40.
`
`@ BET speciics surface ares of a composite material
`
`Below 86-29 is [| mare than mag ] preferable. The BET spsciic suyfane area of a
`compositematerial refers to the surface area of a 2 partie per 7} g of compositematerial,
`
`and is massured by gas adec:oe method When the SET seeaific surface area of the
`nee finely digpersed, and ihe conductivity of {he composite maternal may decrease and
`
`composite material is ioc small, 6 large amount of aiicate parigdes may be grawn and
`
`

`

`ihe dischame capacity may decresse, Wheat the BET smectic surface area of the
`commasite material & excessively large, it becomes difiautl to handle and the elecirade
`density may decrease.
`
`{0032}
`The pore vollene per 1g of the compositematerial is greferably fram O.07 ec fg te 0. oe
`eo?1S more oeeferaily from GOT oo / gt 208 ce ya and evan mone preferably§front
`ce iq te G65 ses g. THs sore volumeis measured
`as adeomion. Ff the pore
`
`volume 8 tooamel, permeabiky of the alectraiyis decreases, and ion conductivity
`uecreases, and there i¢ a posaibittythal the rate characteristics and the Datery capacity
`decrease.
`
`0033}
`(Manufacturing Method of Composite Material}
`
`in the method fer producing @ compose maternal ef the present invention, an anergy
`awppication step, a granulation step, ard a heal reatment step are performed. in this
`
`manufacturing, eeefrst, in arp anergy eenestep. a campound maw material
`
`
`which iS. a nawmaternal of a (Rhlun siioaie-hasedcompound is mixed with a carbon new
`
`material which is a raw material ofa carbon material. Ned, in @ granulation step by spray
`
`doying such as spray drying, a primary paricle is farmed bycoating a slurality of primary
`
`srimary particle by coating the periphery of a compound raw
`particles white forming €
`matedal wih @ carbon raw material, and @ 8 particie is granulated. Then, in the heat
`
`freaiment step, 2 Wihlumsiieebe-based commaund is generated fram the compound raw
`
`material At this me,@siigie ghase of Ihe Milunm Siicake compound is preferably
`generated,
`
`aca
`in the heat treatment step, a carbon material mainiy becomes a carbon material
`containing 4 carbon element by a fhennal decampositien, @ chencal reactionor ihe like,
`
`and @ carbon maternal manvaine @ State in witch a surfaceof 3 lithium silicate compound
`
`ig coateel. For thig ragson, particles coated with a carbon coating layer made of a carban
`madicate compound.
`
` material are formedanthe surface of a sNicate core madeof a it
`
`This particies aggregateas primary panicias to form 2 particies.
`OSS}
`Acourding to ihe present manuiactuting method, he Surface of a fine silimete core made
`
`ofa lithiumsitcatep Sampis Cogied with &oey Sonductive carba8 costing faayer to
`when the composite materialatproducad by the present manciacuring method is used as
`& posilive glectods active substance for a battery, 2 can extitat excellent charge ani
`
`

`

`ciecharge characteristics, In addition, & canposite material can be manufactured by 3
`simple process using a raw material of 6 ithiurn siicate-based compound and a raw
`matedal of a carbon material @a starting materigis,
`
`{S036}
`in the anergy application step, a mechanical energy is aoglied to @ raw material of a
`compound, which is a paw ovateral of a lthken siicate-based compound containing
`Sthiunt (43), sion(Sh and gxygen 6), anc a caren nawmateriahin Gee presence of @
`solvent, By aooiving the mechanical energy, the compound rawmaterial and the carbon
`raw material are mixed io obtain a mixed naw material, The compound ney matenal and
`the carbori raw matenal may $e simply mixed by anotying mechanical energy, hut may
`
`be pulverized ane mixed.
`
`{OOS7}
`
`in the energyapolication step, a mechanical enemy is applied to the compound raw
`
`matioral and the carbon raw material it a Slats of being brought ive contact with ihe
`solvent, Af itia Ree,is preferable that the carbon raw matesal is dissolved in the
`
`solvent to cover the periphery of the compound raw matedal, Further, by applying
`mechanical STuNgy. tis preferaiie that the compound raw material is pulverized and the
`carbon maw matenal covers the surface of the pulverized cammpoundraw material. Thus,
`ihe compound raw maternal and the carbon raw materaresuMiciantly mixed.
`{OO38]}
`
`TRS snerny aodination sien may be & step of applying mechanical energy dy Hing.
`
`Thus, mechanical energy can be unifentlyapplied te the campound raw material and
`the carben raw matenal, ANhough there is ne particular hivetation oan the milling method,
`
`
`various miling methods such as bad miting and bead naling may Se emiioyed. Te
`orovide a method for imparting mechanical anergy to a compound raw material and a
`Gardon raw matedal
`
`if fhe carmpourel raw material ane or the carbon rawmaterial ig mslatively large, tis
`preferabic to roughly grind the compoundrawmaterial and the carbon rawmaterial using
`
`fara Miameter balls or beads. Since a large diameter ball or bead has arelativelylarge
`
`cfushing ferce, the grinding effsot is Nigh anc the grinding siep can be offionently
`performed. His then acdwasble fo use balls ar beads oflarge diameter and then finely
`grind (heni using satadiameter bats Gy beads. With small diameter balls ar beads, itis
`possible £9 grind coarsely ground compound raw material and carbon feedsteckinte fine.
`
`and union particie sizes.
`fOO39)
`
`

`

`‘The magniticis of mechanical energy and the mdling time given by milling depend on the
`size of the compound rawmaterial and the carbon faw material and an ihe ball or head
`matedal gud {he like. For example, when beads made of eiconia having 8 diameter of
`
`VIN} pom are used,is preferable thal the amount of mechanical energy obtained by
`ming 7 beads is fom ® 10.8.) 6 196» 1043.) The fini for anelying mechanical eneny
`iS preferainy } hours or more and 5 hours ac less. H the magnitudeand / or nuling tine
`of the mechanical anergy is foo small, mixing of ike compound raw material may be
`msufficiant, H the magnitude anc / or miling ineof the mechanical energy is too large.
`then bnpuritiesframihe Oaff or beads maybeincorporated.
`fo040}
`
`in. the energy apotcation sep, tor example, & compound rawmetenal and @ carbon raw
`
`wigterial can be mixed is an inert gas ahriasnhere farion gas. niragan gas) ar an air
`
`aimosphere,
`
`OOS}
`The application of raechartical snergy 8 carried outin & solvent. THsis for smoothly
`
`ming and punenang the compound raw material and the carbon rawmeterial. The
`
`
`scdvent uae is mot particularly invited, but is preferably a watersoluble loud such as
`
`water, ethanol, or acetone. The anmurt of the solvent! addedis preferably fram 150 parts
`
`Sy mags fo 800 paris by mass, based on 100 parts by mass of the mixed raw material
`Somprising the compound rawmaterial and eecarhan rawmaterial,
`fOO42)
`
`Soh af the campound raw material and ie carbon rawmaternal {0 which the Mechanical
`enemy is applied are raw matedais of the comipadite material. The oempound raw
`material
`ig a sawmaterial capable af forning a Bthluni silcate-based compeaund
`seniaining ittium (Ls), sieon (St and aeyger (O}. fis prsferaive that ihe compound raw
`wateral Sa raw material
`4oapeine of farming 4 ltheiitete-based carnpound
`io
`represented by the general fo