nature materials PV ane) Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids Keith R. Paton et l.! “To progress from the laboratory to commerisl applications, it wl be necessary to develop industry sealable methods ‘te produce large quantities of dafec-re graphene. Here we show that hghrshear mixing of graphite in sltablestabilzing auld results large-scale exoation to give dlapersions of graphene narosheets. X-ray photoletron spectroscopy and Raman spectroscopy show the exflnted fakes to beuncaiized and free of ea-panedetetts. We have developed sinple ‘model that shows exfoliation to occur once the local shear rate exceeds 10". By uly characterizing the scaling bohavi the graphene production rte, we show that exfolation canbe achieved in guid volumes frm hundreds of mites up hundreds of litres and beyond. The prphene produced by this method performs well In appliations fom composites 0 onductve coatings. This method canbe applied to exfoliate BN, MoS, and a range of eter layered crystals. ing 0 arti tw dimensional (2D) tre and te Unprecedented popes, graphene has Become the most ttolied of mantrneidt. fa the ent doce, pophene veil find commerce aplsion in many aes an igh Frequency dectonies to smartcotings Some Import clsses of pplcaion, such pine electronics conduc costings and orpoate ier wiles nda sae foun of eet ireeganene na poser Force rapes hy to be wend asa lnecot lectode material in Sppiaton sh sna cll tre? and senor Suck lace il aes Cerin be poducd by slong ands wl ue ge Sunita prphene inthe frm old topes nk Slepentans Ino eld elston of gape il Boome Inport technology inthe near future Hower, no walle tmetod exe to gv lage quite of graphene tht alo Ake re For example, wheres oratneelton of graphite an posenaly ge age quae of graphene ike nanosteet fpaphenc nets ply dct’ Athough graphenc xe Proved very scl rn appeatons rom composts to ata Fs very key that an equal wide range of applications wi ree gripe that ie of bal plane dec Alera. Sonteton of gape, o indeed other ijered compounds eran tabling vote raga tanto? get. ‘diet tec nanotbets However he sealable later posse tlimted bythe us of otestion ran energy sour Thin soliton elation methods tend ex ther high prado rts o lw defect contents bat not bh. A dtl Fatt survey (Suplemerary Satin 9) shows that no papers tdci practon ites tbove Oph coupled wih Raman 1G Intern ato amessre of det cone blow Dt the papers surveyed had prdaction ats ow 0.490 tee for commercl production. One pose solution woud be to finds scale method of exflatn that coupled wih he we of Sablsing gue oad ead to re scale praptone produc. Here, we demonstte highshear_ming(Seplementry Section 1) 35 Saale trate wo sone fo the exon of layered esta ach as graphite Shes mining lady wdly ted to disperse nanoparticles in Iga However In generat thes imac breaking up of sanoparte agglomerates" et ae seat found compared with the nthe! Binding strenght Im gaphte A number of papers and pens ave describ ‘pelods or the aliation of graph or ayer compounds at Incprorte shear mining gat ofthe ogy meen al meget Hea mas uP ate Mich hme han Sica weakening the near binding sent” "Under (Qe cremrines deat mtting com be ta texte the ‘tl to ge der nanosecte: Howercr sch methedooges Jan ahi te rate lanating step from extn to inlet, Aiming he pte or sale p Mach more fal would be the silt etl ntete yered crystal In gud sing ony ‘Heat mining The wuld ll the application othe wel ow ae fr the vale ap of shearing process that are oma wed in dustry” However ast ance se ming ‘Save scemsam unl endiatefor eclton of lpeed erste ‘When singalrsonie presto ext raphe, energy denates thousand of wats per lite sre yp used Labora sele ‘ear miners eye dle hundreds of wats into fev les ‘lg eesuling in powder desis af “10011 Ths, ove Soul ezpectexolaion undersea to cer ot ora all orto Jroveed ts much lower te then soniaton ndaced exiliaton, Ffoweves a recent paper as shown tat grphite con be etlitd {ogi prapene by generating hear ery tn gud Lye {rapiy routing tube" Howeves ths maths ge very sal ‘quanies of graphene and tery nscale Here we ‘Ecce 2 metod for shear exflaion of graphite to ge aphene tht (many timer more eft than sonia fat Sek can be sel apo ainsi! Tee We show tht heat ‘Molton can produce lage quantities of df re, unos faphene and devdop 4 model tat quantiaely describes the ‘sf appctions nd the mend can be wed elt nero ‘er jered estabARTICLES “any 4 . =, = . WAY a a AMM ie OS ° a ld ° metonent anes eure rotuconctgaphre yaar mg Sharon ms Shhh rth ming hain aS karl gaphin ioe Podcast a Wien TEA rape SU otc er canton) TEM nage il anne, ‘atioe tot an marly gt nace bye aca atan atrn (gina os mone aged Mohs ‘auane TEMA aan sree crease rene eM ont feet ore. Th prec of rare at or! bysomancuraceranten (ra i 3 and nan seca UMP ole age) meaaaeson bine NM Roman rd XS sre ‘er pts en persis mde vg butadiene hen racers pret seeping oer ppery Seton) Te duperntontype undead pre torneo edd om aan XS ed Nate ar la td vr Bare We mmr ake can | rane ABW suran ed dupes andseed tom foranora Nec dein (Sipps Seton 3d faction PS pcm acne wiht i fms Raman ards The err 5 ‘eomartne store soc ith mie emarement (100 er APfand Ofer aman Uniss rte erie eater ero ‘hea exfoliation ‘Shor nig efron ode LSM miner hat generat high shear anngsceely spaced (10m) rors combination (Gig band Sapiemenary Section 1), ands avalible wt ange froordiameter(p Ibe) nl as led theses ng ‘ot graphite Boh in he save N-metyt’2 pyrrolidone (NMP) Sud in aqueous Stic sluions (ollum cholate, Ne) elnino wlumespersions Fig and Sarpementay Seclons 3, iil procesing paren rr dames Desomm: intial graphite. socenaion, CSO mg rising time, #20 min Haul valame, V 45, ror spevd 1 =sto;pim). After cetifgation these suspensions contain Tage quanti of high quale graphene sanoecy cad ‘ome monolayer Fg Te) "ott the fle of ming parameters onthe qulty of set afin rape (SEG). me prepared range of dipesons ting oth NMPand wateNoc:heping all at eo theming frames constant (a bone) bul mai and ring {he remaining one (Soppementary Seton §). These dgesons ‘were sted by trinion econ microscopy (TEM) snd Sami force micoscopy (AFM) To mesure the ke it sed {hikes etre heringt form 100m hick fis tht were Sturaceized by Xray photoeeos specteoscopy (XPS) sed Raman specroneopy (ig i-kand Supplementary Secon 3) TEM. Iemaremene showed naposhcet aes the MAD rane hd AFM ofsurfctant-exflted sample gate pal chee, No of lem than 10 moooayers per manorbet (Ne)~5-8) (Supplementary Section 3). The presence of monelayers was fftmned By Raman speciscopy (Hine) For ls rd fom NMP exiled graphene PS showed no evidence [tendon and Raman spectroscopy reproduc showed 2D ands (Fig. th se consistent wth Np Between 4 and 7 and nsec weak, nar D band (Supplementary Seton 3) ‘he Karan DIG band intensity rato poprtnal to verse tavosect lng” and the DID" band news rao (Sapplementary Section 3) Takes together thee data show the D band tobe dominate by manos elgecotibatonsand anim that bos plane deat are oduced during ext?” (Sapplemtenary Scan 3). Ar shown In Pg thee propertics ‘verre ivan wih eixng parameters Ising that ‘eleifend dete ree grapene cape produced Things bond range of misig conto We oe tha thee faker tne wal Indtingsbbl frm how roduc by sookaton interme ed ult “The exfoliation mechani Content eviton mechani, expcation as Uhaocie, tue high diate eons ere espnsible Aerexioné™, However we found ula nergy depen to be unnecary Pare 24 mape the combinations of and D that reat exon: graphene Is produced pot ely for Turbulent hgh Reynolds number (Re) sears. but sho for ombintons that ge Ree = ND'p i= 10s whee tarulence bot lly developed” (o andy ate the dds and vscosty ‘eepecte), To determine whether prapene cold fe produced Inthe compice sence a turbans, hati ener igh-theat Tamim Tom we sheared graphite and NMP a Coudte (G concn ctindr based tenga el rade R= mm. thiknes =O, rotation equeney of nner all bear fate j= Ru/d, Saplementary Seton 7) TEM coted that apne ws prod wth cancentraton incesing eth me 2b) Inerestngy me ound graphene nthe Cae onlyPonce a Te Seep eo = be ” i . fe] the 0 mG = 7 an A= 12mm omen t + Fare2 Charatan ft exon mechan Sag treated Ne Sate Der Ser swig sod lation ocng oT There sbne eck ne represent ay seeps alee i ety WO eu rep Soe ee re ‘ora > 1085" Coeanoton Gregan paper raved ag Cat fin i ie tin tater ie Oro) dCercenton al ante pcan Sveti oon shen treat areas {15 cand 2m rig in) ho it secrete wth ara ie Man ange reo, ‘oes (GasOrgmst=20"inVniS Ou 2mm) Thee aspen estrada notes) -T00 easements Tred iets fc estn canara gan the pa Te irae poly les ke nase letra sores minima shesrat a, 10 (ig, 25) Howenes thie "atest enough ogi a Re wel within be lamina Dow regime (igs Recap href) sowing trbence toieunnecesry fr extn “o deci wheter a minim shear rte is gerd rurementwe prepared graphenentheshesrmier ata amber (ire N snd combinations Te concentration produced set Tin ising, yoni plated agate shear ate (92ND AR. wee OR the rior stor pa) bt Fig. 2 This uggs Iain shear ete fj 10", lying that the sre ‘olson mechanisor oars in Got lamina sod tbuent tegen, We rte tat al ofthe welexflaed samples in i 28 re cost! th > 10. Things that ony martha ‘an aclee ti she rate an essed proce graphene. We Skmonstate thst Be ire by wing 4 Kenood kitchen Blender to padic raphe Here efliton oat ect the py Fotung he ene bal turbulent shear ate signe Inger than 10 (Supplementary Seton 0, ‘We can understand thse process by modeling exltion as sheaindued Ire sing i seo” (Suppementary Secon 7) This pits mm her ate gier [vBc~ VEST ™ whee Ey and Ey ae the surface energies of grapene and Ngai (Fy 8mm foe NAEP et 1D). te lid cy (017 Ps or NM) and Lith ak gh Ths tion cs ‘Bows the te of the een fr oben eh wee eorgcs alching griphon te exaistion energy ini iain ‘hear exolation a le shee rats.Ginen the fake sie meee bp TEM (~300-800nm) and j= 10s equation (1) pe Fiu=05-71 very cle the expected ale ‘uation (can be erinen wo expe the ini fake sie hat can be produced by shear exlation a2 giv 7 o eee Suinenaiaie 2 Pacer Se aoe eee eee a ul on HIMES ® eee Sanus Aaspiaaaey east Se oh opie Scie ee eet ee ee {AM it ny pte fee orien sition ous la ‘Sealing up shear exfoliation Tes Mmprtant 9 undetand wha contro the amount of gophers proce withthe im of maiming the podton {by scleap. As propels of sheared dpersions end to se with procesing parameters at power nwa the graphene ‘ocentaton sult clea excrenD'y © ‘Totes this we reputed a wie ange of dpenons, comtalaly ‘aryng al five ming parameters These wee enifoped and (he gupbeae Gononifvion mearered opel (Supplmenary Seton 3) Keeping, N-Dand V condant bt varying show Ga hewe ets 1066 (Fp 5} very snr tothe Coute ‘exponent ace above and Saplementary Seton 7}. We ne that[itn he » wl a : 3) A ee = cou wiimsin Be) ¢ . ' i edo |e Peale ‘ere Seng of ppteneredacon sings mie Dope onariaion © (oregon pts fe There det eho pe Ca are ns cones Oc Go he ane aes turstn eo ne ted ae alah concen ft gious V netting eens ven ne ane ernment ints nner baer lent ay raking ag: qu alumes wo ure Gert smit ‘Secs tskershtnga sociale sch al gdh ae tote ener Te spe tte hw gna nah sonication efition graphene inserts 422) ‘genting tat tne exponents cose to .507 may he pre Independent and se epesent more fundamental behviut ‘ieee Catieted inet hove eetinre estar setnga main ming une We oad 0 be proportions VND” gb) quantity rested theme de are toe pape trough theorists once" Meosarement of C ‘as allowed the cealition of» represent cancentation Tererample tat achive ter ism, qn Menareent (Cer diferent combinations of. BGM tad V (Bg et) Showed that power-law behaviour ws obscrved with exponent ffaihd =2280= "Ds When arin N power nv bese {i= 13) was ony observed above anima rpm, New, ch {Stsocitd ith de minimum aerate decried above “A el of hee eling nv the conection dats sould fon maser carve when pated ain te scaling fate CHR Dy ws cote ie It Thee eponen fre ont specie to raphe we pled the concent Mos esate in NMP vers CENT DV at wg the same exponents as graphene in NMP) Sading ress Feary 1) ‘Stes on the bekage of ceramic material note stor nines have suggested «ik between parle concentration ad {al enegy spate pe volume!" The power dpe by 2 Festa mise ven by P=Np XD) where pe the event {egy and =? (rt 2638). Ths expres coupled withthe “aponets metared for mixing NSAP sages ogution (3) ‘rapprniatayequaten 1 Y= C/C ce VETV. whee Y 1 the graphene eld nd Vt the ttl energy disputed per tuntvolume (Soplemeniary Section 8). Plting ¥ versus E/V ns this fo fe approximately true (Fg 4). THs alas us to compare sear exaatn to sencaton indeed ellton (Pig te}shosringsbearesoltonobecndersbly mor ese than ultasonte exon, becoming more sa asthe volume I Sneed (Supplementary Secon 9} In adlon ta Inherent ‘cls, this ret shows tht she exfolation ise mich lage anit of graphene a lower ney cost tha is posible tik saniationindaced elation orth ting tat the {lation its rere wt <0. Hower by eeyci (gape samen ana of he gape can transformed {no graphene (Supplementary Section). Moreover thei might be eahanced mately by eral che ofthe starting grape ‘terial or optimisation the toe or commercial production, the os ipotat parameter 4 with exponents as above: The masinu rodacton cate achieve sp Ibortry alsa Ligh" or hort ming time ar higher thanany te revel achlved or ‘elton processed defect graphene Supplement Section), ‘wl be more sespilorwand to soe up hem exten of faphere In aguceus rte than enn stent environments ‘has orarge sae sud, we cae om elation y mag gue solutions ofthe srfactant NA (ahowghplmes nc ‘tr pavsinglohal can tobe nd see Saplemerary Seton 0 or bot polymer and sification gripe, sag ebaiourwat found Supplementary Sections 42nd withthe at for paphene exflated tt NaC shown in Fig. Hee the slg ‘ponents ave sighy silent wih oe Ge™"N=DOV om relecting mechani ieee ‘hn sea the msig me should be xed at LV andthe roar dameter hea be sad in Proportion tank ne (De ee Supplementary Section 4). Tis pret By ging Pye Vor NMP ad Fee Vor suc, ening that predation rate cam be ners by sling ap ‘he mining volume. We perormed lage-sele eal (4-0 Ing th sutacaneslauon (c= 100 gins C=Smin-th, Nia 3p00rpm, D = em), ah volumes op to ¥ = 301 (opplementry Section 6). Th yelled up 10 2. of ih ‘quay graphene (Raman DG rao of O18) per bach wah SSocetaties ap 62 C007 mpm and production sab high ws Fe =53gh " slgicanty beer tan any reported workTens eo) =| ' go i. fA qe FReme Scng ot shen retin sng shar mie 2 Gnshere cocriron nN ted pitas sinc ‘aa the ceing les ctr ot bP ets conaraonl NaS: AME, ete pin scorer var desng at {Gps ys memard rn erey Seay Asoshoun owen nor hrm sonetes pons od Y=0 22 seheres {Supplementary Seton 6), Both Iaboetor scale and ges ‘Soon dats flee ese sling Iw (te Tis Slower tgesimatethat onsale upto = 10 prodeton eae: ‘xcnlng 100g "ae poss (Spplementary Sections 4nd 6). ‘Xai estar reve shows tht opr! some lato Combination of highpreduction at low Ramm Gras sk ides reported ee (Supperentay Seton) Applications of SEG “The SEG produced has been ceed in 4 range of applkatons ha rege lge quanti of ches et gouty grpene [Sappcmentary Section 10) The mons applesion i Fetforcement of el preted compote. We added 07 wt fuphene to poleivene tecplaste (PET), = common rgincering, pli by melt ming resing Jn. macrncope ‘omponter (ig 5) wih welldipered graphene nanshects {Pig 3b). Even td ow ong ee we ond 0 cee In'eengh and a 13% increae in mode (Pg. Sohn le ‘f renlrcemenc that far surpasses that found for ay ther Bier (Saplemestry Section 0). We produced thin nef gaphene haosheet (Fig) that have conduct sigh 3s {osc (Fg. Se), competitive wi her vludon-peocred fruphene® and sue or decode appicatons One amp I the replicement of the Puindum tin exile seco i 8 Ahesenstaed sla el sul in snr Tees of effin iti 3). Thi ns 25mm) of SC exh» combi of hgh ‘eiraiccapactance at 120 Ir and phase angle ne to {Fig 9g sulle fc ate a kro superespuctrs in toni !inothing apace Thicapuctance's ties higher han sanosraured diets capactor and scompetve wh ch ttt etre exiting ster We he alin pred ‘orl composer by aking commecinly sable cc mans In dspersons of SEG tn NMP rething fo lfson 9 graphene Inte he uric the hss: Tis eerste band conti seth reatance tht depends exponential on stra Sach ans Ina very effecive dynamic sam esos th ow-aln gag fetes of Band eves ange fats 0% supe {commensal met sai gaps” Cig 84) CConcusion and outlook ‘Wehhve emanate lable metodo poducing eatvely Jae qusnies a dtc ee graphene. This as ecleved si igh-herminingstectncogy ht ature salable sed widely crab We have shown thtexlton xcurewhenee tela ‘hearrateeceedea ctl votes found abe 1" Sach ‘hear ate as be atived ss ange of mer nln simple ‘chen benders The graphene produced inthis way stay Indsingistale om that reduced by sonkaton a grophie n toler oeritnt rds been denned to beeen ‘ange fappction from ompotes tose Import ih ‘hear mit ca ho be aed ext une of ter aed ‘eater nding eS, snd BN “Orr the psf ye has show tht alex 20 materia such ss rapene and Moyne eleven wie ‘ageol spicabens om aac baierssFormny a tebe "pplatonscommerclntan wl requ the saa of rg ‘snievofhiph-qut mater This mas the demonsatn af ‘Sse podaction melds for delet fe, 2D trl realyfoe ares ANNAN AAA HAMAR Sa Levan] 2 [Pititio, Pg dh cermin ar on het eoabe ects oo} Ap Aled sin and masa ‘eoblance Jens ncionl eer an estererashere comport ié4éé@é=e—_ _ —rrt—s Metods ia thet eomnnms a ops wh cates, ta oo — 3 elvis hermes eteig "Sma tose my eed pape ep cle an he emeconmea oven emg | ectved 27 Seplemter 207; acepted M March "Ci chpman ling on Pc Sake pubished alte 20 Api 2014 * fei am et a Sh itd tee Referet errant m9 ct certo ‘DMF eated pgs Sts Cho 27378 (OO ini: 20%) 5, Reson chore -kaumldeict sme RCsemn 1X, 2, hone on Sci DA Gogh ene Trantor ede ee e919) ‘pars hg ange a)ARTICLE: Piiteen 2. a 8 at Oat of tubule eating i. Phy Rey MERIC ana ntmtemres Beier rate uens ey Sec eee, {tn wae 208), eat mechan ea po ane pute aes Chen ng es 97, a nS tlan nae garnet oe a oo 1 Eee egecaneoneare aero ores timer Sie Xtal Sanh te goer me a ‘omen etn 29 2, Actnowedeonets ‘etal oa Sierra aes Sane meaner. ee Aditional information Keith Paton, Eswariah Vari, Claudia Backes, Ronan J. Smith, Umar Khay,Arene O'Neill, Conor Boland, ‘Mustafa Lay ana MItate™ Pau king Tom i kbar Abenes, iggins' Sebastian Borich®, Peter May, Pawel Puckarsk, und ong Ho Cochol Sean OBten ios Moebius, Hemi Petersson, Edmund Lang, Jodo Coelho Sean fra K McGuire’ Beatriz Mendoza Sache, Georg. Duesber', Niall McEvoy", Timothy |. Pennycook' Clive Downing lion Cressey, Valara Neoos! an Jonathan N, Coleman "cat tr etch on Adapt Recs ad Nance (RANA Tiy Coleg Db Du 2 ln? 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