(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property = Organization International Bureau (43) International Publication Date == 13 September 2012 (13.09.2012) WIPO| PCT LON 0 (10) International Publication Number WO 2012/120291 Al G1) International Patent Classification: (C2SB 1/00(2006.01) CIB 31/04 2006.01) 21) International Application Number: PCTIGB2012/050487 (22) International Filing Date: 5 March 2012 (05.03.2012) 25) Filing Language: English (26) Publication Language: English (30) Priocity Data: 1104078910 March 2011 (10.03.2011) GB (7) Applicant (for all designated States except US): MOR- GANITE ELECTRICAL CARBON LIMITED [GB/GB]; Upper Fforest Way, Morriston, Swansea, West Glamorgan SA6 8PP (GP), Inventors and Inventor/Applieant (for US only): STIRLING, Chri topher [GBIGB]; c/o Morganite Fletreal Carbon Limited, Upper Fforest Way, Morriston, Swansea, West Glamorgan 'SAG SPP (GB), ‘Agent: PHILLIPS & LEIGH; 5 Pemberton Row, London EC4A 3BA (GB) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, m2 3) ) a (34) CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, BS, Fl, GB, GD, GE, GH, GM, GT, HN, HR, HU, 1D, IL, IN, IS, JP, KE, KG, KM. KN, KP. KR. KZ, LA, LC, LK, ER, LS, LT, LU, LY, MA, MD, ME, (MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, , PL, PT, QA. RO, RS, RU, RW, SC, SD, SE, SG,'SK, SL, SM, ST, SV, SY, TH, J, TM, TN, TR, Designated States (uriess otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, UG, ZM, ZW), Furasisn (AM, AZ, BY, KG, KZ, MD, RU, 1, TM), European (AL, AT, BE, BG, CH, , DE, DK, FF, ES, FI, FR, GB, GR, HR, HU, IE, 18, 17, LT, LU, LV, MC, Mik, MT, NL, NO, PL, PT, RO, RS, SE, SL SK. ‘SM, TR), OAPI (BF, BI, CF, CG, Cl, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, 76), Declarations under Rule 4.17 4s to applicant's entitlement to apply for and be granted a patent (Rule 4.174i)) of inventorship (Rule 4.179) Published: with international search report (Art 21(3)) {Continued on next page} (64) Title: ELECTROLYTIC EXFOLIATION OF GRAPHITE Figure 1 ‘duced according to the technique wo 2012/120291 A1 [IIIT (87) Abstract: An electrolytic technique for exfoliation of grap closed electrode material to yield unexpected results, Intercalated graphite particles comprising gradation of expansion may be pro- is presented. The electrolytic technique utilises a previously disWO 2012/120291 A 1 /MITINININ NG INN UNA AT = before the expiration of the time limit for amending the claims and to be republished in the event of receipt of ‘amendments (Rae #8.20h))WO 2012/120291 PCT/GB2012/050487 Electrolytic Exfoliation of Graphite This invention relates to graphite and graphene species. Background Graphene materials and other graphite nanoparticles are of interest for use in a number of applications, including energy storage and conductive materials. A number of methods have been developed to produce graphite nanoparticles, including micromechanical cleavage, epitaxial growth via ultra-high vacuum graphitisation, chemical synthesis through oxidation of graphite, chemical vapour deposition techniques, and solvothermal synthesis Wang et al (Carbon 47 (2009) pp. 3242-3246) have reported a technique for producing graphene nanosheets via electrolytic exfoliation in ionic liquids, using high purity graphite rods as electrodes, Amongst the benefits of such methods over the more commonly acid intercalation methods is that they do not necessitate the use of dangerous and environmentally harmful chemicals as part of the process. Another electrolytic technique is disclosed in the material presented by Liua et al at http://practice.nenu.edu.cn/kycg I/lunwen/56.html (website retrieved 22/02/2011). An electrochemical method to produce nano-scaled graphene platelets is disclosed in US. ication no. US2009026086 (A1) where a bed of graphit dispersed in electrolyte is electrochemically intercalated to produce a graphite materials patent appl intercalation compound. Geng et al (Journal of Nanoscience and Nanotechnology, Volume 11, No. 2, February 2011, pp. 1084-1091(8)) also cite a method for electrochemically intercalating graphite to produce graphite intercalation compounds. In both US2009026086 and Geng et al the graphite intercalation compounds were subsequently expanded by, for example, thermal or microwave treatments. An alternative approach to manufacture of graphene is to use kish graphite and mechanically exfoliate it. Kish graphite is a by-product of some iron making processes. Kish graphite typically has high crystallinity but high impurity levels and requires acid leaching to get products with less than 5% impurities.WO 2012/120291 PCT/GB2012/050487 Summary of Invention ‘There is a recognised need in the art for means of improving the yield and the quality of graphitic nanoplatelets yielded by electrolytic exfoliation methods, preferably without incorporating the use of dangerous or environmentally harmful chemicals. ‘The present invention makes use of electrode materials comprising aligned graphite flakes (natural or synthetic) bonded with a binder, such as (but not limited to) the carbonised residue of a mesophase pitch, in order to attain an unexpectedly high yield of quality nanoparticulate materials, The PCT application publication no, W002/090291A1 discloses such a graphitic body incorporating flakes with a flake size of at least 200 jum ~ page I, lines 21-28 of the publication in particular discloses one method by which alignment may be achieved, though the skilled person will appreciate that it ikewise, the PCT is not the only method for achieving alignment, application publication no. WO2007/063309A1 discloses another such material suitable for use as the electrode material in the present invention. In W02007/063309A 1 too, the binder may be the carbonised residue of an organic precursor [for example a mesophase pitch]. The skilled person will appreciate that these two examples are not the only electrode materials that could meet the requirements of the present invention. ‘The scope of the vention is as set out in the appended claims. Description of Figures Figure | is a scanni 2 electron microscopy image of a graphite species produced according to the present invention, Detailed Description Electrolytic tests were performed using an electrode material comprising aligned graphite flakes in plate form (so-called “K-plane” or “K-p” plates), using a 0.001M aqueous solution of poly(sodium 4-styrene-sulfonate) as an electrolyte solution and a similar DC voltage to the experiments disclosed by Wang et al (Carbon 47 (2009) 3242-3246),WO 2012/120291 PCT/GB2012/050487 ‘The aligned graphite flakes in the K-plane plates were Graphite V-RFL 99.5 +500 a 99.86% pure natural graphite available from Graphitwerke Kropfmiihl which has a flake size distribution [% by weight > than specified sieve size]: 30%>800,m, 77%>630,m, 95%>500,1m, The flakes were bonded with a binder comprising than specified sieve size]: 50%>200m, 25¢>355 jum] did show evidence of expansion, but much reduced from the amount shown on acid intercalation as is discussed below.WO 2012/120291 PCT/GB2012/050487 ‘The directly-expanded graphite species exhibit topological features that may be of interest for certain applications. The accordion-like structures (e.g shown in Figure 1) exhibited a “fan-like’ appearances, indicative of a gradation of expansion throughout the intercalated particle. This produces a structure with increased surface area that is accessible to fluids, but still maintaining good connectivity between the expanded sheet. This is expected to offer advantages over graphite materials expanded by other methods, for applications such as energy storage or adsorption. In addition to the directly-expanded graphite species’ own properties, the species may be a useful precursor to other graphite species. As is discussed above, small thin flake-like graphite particles may be produced from the directly-expanded graphite species via ultrasonication and mechanical methods of producing such small thin flake-like particles from the directly-expanded species may also exist. Subsequent to the above experiments utilising the ionic poly(sodium 4-styrene- sulfonate) as an electrolyte, a new set of experiments took place in which the “K- plane” plate electrodes comprising aligned graphite flakes bonded to a binder were utilised with a 4.5M sulphuric acid solution as electrolyte which yielded surprising results. ‘The first experiment took place with an applied potential of 6V and resulted in a large amount of gas evolution at the negative electrode. Generation of particles at the positive electrode took place immediately. After 3 minutes the applied potential was reduced to 3V; gas evolution was significantly reduced as a result. After 10 minutes significant attack of the positive electrode was noted, especially at the plate edges though particles were not observe to lift from the electrode surface. At 10 minutes the voltage was increased to 3.5V, and there was a notable increas n evolution of gas at both electrodes. By 17 minutes particles were free in the solution and were floating to the solution’s surface, By 25 minutes the particles had bridged the two electrodes. Particles in a sample taken from the solution at 27 minutes showed clear signs of expansion, and so as in the experiments utilising the ionic solution electrolyte (theWO 2012/120291 PCT/GB2012/050487 poly(sodium 4-styrene sulfonate solution) direct production of expanded graphite species had occurred. At 45 minutes the test was concluded and the materials washed and dried. It was noted that the positive electrode had lost 1.01g, but the dried powder recovered from the solution ws ighed 1.75g, indicating that a significant amount of intercalation had taken place. An attempt was made to further expand the graphite species produced by the experiment via thermal methods through the use of a Bunsen bumer flame. Whereas the expanded graphite species produced utilising the ionic liquid electrolyte were not observed to expand further utilising such methods, the expanded graphite species produced during these sulphuric acid electrolyte experiments yielded a surpris 1g amount of expansion. For example some materials produced “worms” of expanded material of the order of 20mm or more from starting graphite particles of 50um or less indicating an expansion of the order of 400X. ‘Three experiments, experiments 21, 22 and 23, took place subsequently to this. These experiments again utilised an aqueous solution of 4.5M sulphuric acid as an electrolyte and the K-plane plate electrodes comprising aligned graphite flakes, bonded to a binder, The electrodes were dried at 110°C and weighed prior to the experiment. At the end of the test the plates were washed and loose surface particles were removed. Particles in the electrolyte were washed, filtered, rinsed and dried at 110°C. The results and other parameters of these experiments are given in Table 2 below,WO 2012/120291 PCT/GB2012/050487 ctrolys ulphuric acid electrolyte, Experiment Summary z 22 - ne 21 | Graphitised K-plane [3 [45 [42 _ | positive [19.00 061 negative _| 19.31 2 | Carbonised plane [3 [45 [40 | positive | 1805 055 negative _| 1804 23 | Graphitised K-plane [33 [30 [40 | positive | 19.41 9 negative _| 1897 It was observed in the above experiments that the higher voltage (3.5V vs 3V) gave a higher rate of material ejection from the electrode and higher rates of gas evolution. It was also observed that the particles floated almost exclusively to the surface of the solution. The applicant believes that the gas evolution helps detachment of particles from the electrode surface, exposing fresh material for intercalation, It was also noted that significant attack of the positive electrode occurred on both of the major faces of the plate (the two larger faces). The attack was more pronounced on the “inner” face (the face of the positive electrode facing the negative electrode) than on the “outer” face (the face of the positive electrode facing away from the negative electrode). This was also observed in the tests in the ionic liquid electrolyte, was more but in those tests the difference in attack between the inner and outer fa pronounced, whereas in these tests with the sulphuric acid electrolyte the difference is less pronounced It is evident that the intercalation and generation of particles from the K-plane plate electrode comprising aligned graphite flakes bonded to a binder occurred at a very ing an acid electrolyte. It will be evident much greater rate in these experiments utili to the skilled person that other electrolytes used in acid intercalation processes may be utilised with the K-plane electrodes as well.WO 2012/120291 PCT/GB2012/050487 10 Iti iso notable that the experiments utilising the sulphuric acid electrolyte yielded graphite species which could be expanded subsequently to a significant extent. This is a major difference when compared with the graphite species produced in experiments utilising the ionic liquid electrolyte, (It will be obvious to the skilled person that any method utilised to expand graphite subsequent to acid intercalation could be applied.) This implies a high degree of intercalation, which may be expected to be advantageous for obtaining high yields of thin graphite nanoplatelets after chemical reduction The formation of graphite intercalated compounds is also indicated by the overall weight gains found in the materials Experiments were further conducted to electrochemically exfoliate materials comprising aligned kish graphite particles in a binder comprising the carbonised residue of a phenolic res This material does intercalate and produce flakes which detach from the electrodes, but does not expand as much as materials using aligned natural graphite in a binder comprising the carbonised residue of a phenolic resin. Applicant hypothesises, without wishing to be bound in any way, that this may be due to high crystallinity or aspect ratio or both. It will be evident to the person skilled in the art that the above examples are illustrative only and variations and modifications may be made while falling within the scope of the claims.WO 2012/120291 PCT/GB2012/050487 rt Claims 6: A method of producing intercalating, expanded, and/or exfoliated graphite or graphene species comprising the step of electrolysis utilising electrode materials comprising graphite, characterised in that the graphite layers of the graphite are oriented within 20° to the plane of a surface of the electrode. A method as claimed in Claim 1, in which the graphite layers are oriented substantially parallel to the plane of a surface of the electrode. A method as claimed in Claim | or Claim 2, in which the surface of the electrode which the graphite layers are oriented in respect of is the surface with the largest surface area. A method as claimed in any preceding Claim, in which said surface of the electrode has a diameter of at least 10mm. A method as claimed in any preceding Claim, in which the electrode material comprises aligned graphite flakes bonded by a binding material. ‘A method as claimed in Claim 5, in which the binding material is a mesophase pitch. A method as claimed in Claim 5, in which the binding material is a phenolic resin, A method as claimed in Claim 5, in which the binding material is carbonised or graphitised. A method as claimed in any of claims 5 to 8, in which the flakes have a flake size of no less than 200 jum.WO 2012/120291 PCT/GB2012/050487 12 A method as claimed in Claim 1, in which the graphite materials may be selected from natural graphite, synthetic graphite, highly orientated pyrolytic graphite, graphite fibre and highly oriented graphite tape. ‘A method as claimed in any preceding Claim, comprising the additional step of ultrasonicating the graphite or graphene species produced subsequent to the conclusion of electrolysis. A method as claimed in any preceding Claim, in which the electrolysis takes place in an electrolyte comprising an ionic liquid, A method as claimed in Claim 12, in which the ionic liquid is an aqueous solution of poly(sodium 4-styrene-sulfonate). A method as claimed in any one of Claims | to 11, in which the electrolysis, takes place in an electrolyte compr jing an acid solution. A method as claimed in Claim 14, in which the acid solution is an aqueous sulphuric acid solution. A graphite or graphene species produced according to the method of any preceding claim. A graphite species comprising intercalated graphite particles, characterised in that there exists a gradation of expansion within the intercalated graphite particles, A graphite species as claimed in Claim 17, further characterised in that the graphite particles possess a fan-like shape. A graphite or graphene species produced by further treatment from the graphite species of Claims 16 to 18.WO 2012/120291 PCT/GB2012/050487 20: B A graphite or graphene species as in claim 19, in which the graphite or graphene species is produced by exposing the graphite species of claim 17 or 18 to ultrasonic vibration, A graphite or graphene species as in claim 19, in which the graphite or iphene species is produced by expansion of the graphite species of any of Claims 16 to 18.WO 2012/120291 PCT/GB2012/050487 1/1 Figure 1INTERNATIONAL SEARCH REPORT International application No PCT/GB2012/050487 Ie SBT /G0 "ote 31/04 ADD. Acsordng o International Patent Ossafeaon IPO) er tbethnatonal elation and IPC Timo socurertatonserahad (SusefcaTon system flawedby SareTionion STOR) C258 CO1B ‘locos da base coneued dura The Plaratonal searah (name dala base and, where pratoaile, sarah Wve used) EPO-Internal (DOCUMENTS CONSIDERED TO BE RELEVANT Category” | Olson of oeurent wh heaton, where appropri, of he relevant panagee Revert cinta x CHING-YUAN SU ET AL: “High-Quality Thin 1-4,10, Graphene Films from Fast Electrochemical 11, 14-21 Exfoliation", ACS NANO, vol. 5, no. 3, 20 February 2011 (2011-02-20), pages 2332-2339, XP55030001, ISSN: 1936-0851, DOI: 10.1021/nn200025p Y "Results and Discussion" 5-9 “Experimental Section"; figure 1 X] Further documents are ated inthe contruation of Box Di] span ne ~Spesalcaegorce of oted doauments ‘obo of pari mavanee sari: ppestion optet but planes ono ater he tran Sted enaotah te puctaton dae arater thon or ter Special reason (as soeathed) "0" document refering oan orl dsosure, use, exhbtion or other “F eeement pba pote tara fing dt but terthen st and notin cons with he appeaton ut etd To undertand ‘he panels or theory unserying be vention, ‘onadered hovel oeannot be conaderedto ive an vente SMtpwhon the document taken lone “Y dosumentf partulrrelevanos; he claimed invention sant be ‘anaderadfofalvean invents slep when the socuvert Somos wih one or mote cine uh documents, sun combination Sting dvious o's person sted nthe a ‘Date a th aul completion ofthe htemalonl seach 23 August 2012 Date ofmaing othe Wamaonal seach report 30/08/2012 ‘Namo and maling adres ofthe ISAT Tel 31-70 340-2000, Fax (a7 03016 Thahoraed fier Hammerstein, 6 Fam POTENT fase hen ONOINTERNATIONAL SEARCH REPORT International application No PCT/GB2012/050487 ‘iCantination), DOCUMENTS CONSIDERED TO BE RELEVANT Ccateg007 ‘Ctaton of dosument with inceaton where appropri, of he relevant passages Relevanto aime, x LEE SH ET AL: "A graphite foil electrode covered with electrochemically exfoliated graphene nanosheets", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 12, no. 10, 1 October 2010 (2610-10-01), pages 1419-1422, xP027423679, ISSN: 1388-2481, DOI: 10.1016/J. ELECOM.2010.07.036 [retrieved on 2010-08-04] the whole document US 2004/131533 Al (SPACIE CHRISTOPHER JOHN [68] ET AL) 8 July 2004 (2004-07-08) cited in the application paragraphs [0112], [0260]; claim 45 GENG ET AL: "Effects of Stage, Intercalant Species and Expansion Technique on Exfoliation of Graphite Intercalation Compound in Graphene Sheets", JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, AMERICAN SCIENTIFIC PUBLISHERS, US, vol. 11, no. 2, 11 February 2011 (2011-02-11), pages 1084-1091, xP009162134, ISSN: 1533-4880 cited in the application figures 5a,5b US 7 658 901 B2 (PRUD HONE ROBERT K [US] ET AL) 9 February 2010 (2010-02-09) column 4, line 66 - colum 5, line 26 US 6 406 612 B1 (GREINKE RONALD ALFRED {US]) 18 June 2002 (2002-06-18) colum 1, lines 34-50 1-4,10, 12,13, 16-21 5-9 5-9 16-21 16-21 16-21 Fam PETER nn ein aINTERNATIONAL SEARCH REPORT International application No mation on patent family members PCT/GB2012/050487 Patent cooument Prbleaton Patent family Publeaton cited sarah report cate members) cate US 2004131533 Al 08-07-2004 CA 2448806 Al 14-11-2002 CN 1524066 A 25-08-2004 EP 1385802 Al 04-02-2004 6B 2375501 A 20-11-2002 JP 2004527448 A 09-09-2004 NX — Pag3009888 A 17-02-2004 US 2004131533 Al 08-07-2004 02090291 Al 14-11-2002 US 7658901 B2 09-02-2010 CA 2623451 26-04-2007 CN 101287679 A 15-10-2008 EP 1934139 Az 25-06-2008 JP 2009511415 A 19-03-2009 KR 20080059571 A 30-06-2008 US 2007092432 Al 26-04-2007 US 2008302561 Al 11-12-2008 US 2008306225 Al 11-12-2008 US 2008312368 Al 18-12-2008 US — 2009053433 Al 26-02-2009 US 2009053437 Al 26-02-2009 US 2009054272 Al 26-02-2009 US 2009054578 Al 26-02-2009 US 2009054581 Al 26-02-2009 US 2009123752 Al 14-05-2009 US 2009123843 Al 14-05-2009 US 2009127514 Al 21-05-2009 US 2011052476 Al 03-03-2011 US 2012088084 Al 12-04-2012 2007047084 26-04-2007 US 6406612 Bl 18-06-2002 Fam PETER ae ay ano) RPT)