US10505193graphene PDF

«2 United States Patent 1US010S05193B2 IS 10,505,193 B2 (10) Patent No.: Tour et al. (4s) Date of Patent: Dee. 10, 2019 (54) LASER INDUCED GRAPHENE MATERIALS (58) Field of Classification Search AND THEIR USE IN ELECTRONIC DEVICE CCPC se HOIM 4/366; HOIM 4587, HOIM 41628; HOIM 4643; HOLM 10/0525; HOTM (71) Apolicent: WILLIAM MARSH RICE 10054; COLB 32/184, COLB 2204004 UNIVERSITY, Houston, TX (US) C08 73/10, COLP 200540, HOIG 11/06 HOIG 1136; HOIG 11/68; Ho1G 11/70; (72) Inamon: Jame Me Tw, Bl TX ‘YORE 601s See application file for complete serch history Peng, Houston, TX (US); Carter a a Kittrell, Houston, TX (US) 66) References Cited (73) Assignee: WILLIAM MARSH RICE UNIVERSITY, Houston, TX (US) USS. PATENT DOCUMENTS (*) Notice: Subject to any dischimer,theterm ofthis —$978391 A 11099 Das etal patent is extended or aijsted under 38 SU7S864 BD 122011 Choi Ba2v 3000 US.C. 154(b) by 445 days. AB aas ny AS day 206017617 AL $2006 Geka 5 : 20100095595 AL 42010 Prat Hone t (21) Appl. No ISMI9S16 201010284156 AL 11/2010 Tour et al . " do1200s895 AL 32012 Lin 22) EC Ee gg Pe 12a ay 2120196074 AL* 82012 Ago BEY 30000 st (86) PCTNo: — PCTIUS201S/16165 20120258587 AL 102012 Kubet al $371 XD, (Continued) (2)Datsr "Aug, 17,2016 FOREIGN PATENT DOCUMENTS. (87) PCT Pub. Nox Wo20IS/175060 ox to1sarm07 A 22a PCT Pub, Date: Now 19, 2018 wo woapimies © "aan (Comtinved) w) Prior Publication Data Us 20170062821 AL Mar. 2,2017 OTHER PUBLICATIONS send Foes Sech Report for EPLST3H09.2. dan 29, Related US. Application Data 2018 a (Continued) (60) Provisional application No, 61/940,72, led on Feb 17, 2014, provisional application No, 62105,380, filed on May 30, 2014. Primary Examiner — Anca Eoft (1) Int.c (14) storney, Agent, oF Firm — Winstead PC MOIM4587 201001) mows 432 (2006.01) sm HOIM 4/66 (2006.01), 7 een HoIM 19ws25 (201001) In some embodiments, the present disclosure pertains to m01G 1106 201301) sthods of producing « giphene material by exposing arene een polymers ase sure In some enbaiens, the expos ce ae) ing rss infomation of «graphene from the polymer. In Peis lesan some embodiments, the methods ofthe present disclosure coaaiaas fewemy abo include a stp of separating the formed graphene from merci Gorse the polymer to fom an slated graphene. In some emo HoIM 436 (2006001) ments, the methods ofthe present disclosure also ined @ mows 190ss (201001) Step of incorporating the graphene material or the isolated ( US.CL sraplene into an clcronic devi, such san energy storage CPC orn. HOEM 4887 (2013001); COMB 32/184 device. In same embodiments, the prophene i uilized a at (2017.08), Co8G 73/70 (2013.01), HOIG 1/36 (2013.01); HOG 1168 (2013.01); HOLM 4/366 (2013.01); HOIM 4/625 (2013.01); HOLM 47663 (2013.01); HOLM 10/054 (2013.01); HOIM 1470825 (2013.01), (Co1B 2204/04 (2013.01), COIP 2006/40 (2013.01); HOIG 11/06 (2013.01); HOG 11/70 (2013.01); YO2E 60/13 (2013.01) Teast one of an electrode, cureat collector or adkitive inthe electronic device. Additional embodiments of the present disclosure pertain to the graphene materials, isolated gra phenes, and electronic devices that are formed by the rthods of the present disclosure, 45 Claims, 63 Drawing SheetsUS 10,505,193 B2 Page 2 (56) References Cited US. PATENT DOCUMENTS: 20120264207 AI* 102012 Shape Gane 1733, 435007. 201200265122 AL 102012 ELShal ta 201310008399 AL 42013 Bhan ta 20130230709 AL 92013 Zhou al 20130238809 AL 92013 Ruoffet al 20180273260 81% 102013 Chick RY 31000 27885 201310298367 AL 12013 Compton ea 20140212506 AL* 72014 dbangir-Fameniah Bey 1000 27581 FOREIGN PATENT DOCUMENTS. Wo woos 8203 Wo Wo21s0008 = 12018 Wo | Wo20I6IS71 $2016 (OTHER PUBLICATIONS ‘Ofce Acton for Isl Patent Application No. 247294, dated Feb. 27,2018 Oce Acton for Chinese Patent Application No, 201580019802 X, dated Feb. 6, 2018 International Search Report and Wren Opinion for PCTUSIS 16165, dated Doc. 28, 2015 International Preliminary Report on Patentability for PCTIUSIS! 16165, dated Sep. 1.2016 Pech, Ds Brune, M; Duoa, H. Huang, P; Mochalin, Vs Gogets, Y¥ Tabera, PL; Simon, P. Uliahigh-Power MicrometeSized Supereapaciors Based on Onion-Like Carbon, Nat, Nanotechnol 2010, §, 681-654 ELKady, M, F; Kane, RB. Scalable Fabrication of High-Power Graphene Micro Supereapacitors for Flexible and on-Chip Energy Sorage. Nat. Commun, 2013, 4, 1475 HL-Kady, M-F; Suong. V; Dub, S: Kane, R.B. Laser Seibing of High-Perfoomance and Flexible Geaphene-ase Electrochemi- «al Capacitors. Science 2012, 335, 1326-1330 Zhu, ¥; Murali S Sole, M.D; Ganesh K; Cai, W: Fee, 4s Pile, A; Wallace, RM; Cyehos, K. Az Thommes, ML ‘Gabon Base Supecspaitor Produce by Activation of Graphene. Science 2011, 332, 1537-1541 ‘ang LL; Zhao, X, Caron Based Materials as Suprcapacitor letodes, Chem. Soe. Rev. 2009, 38 (9), 2520-2531 Wu, Z. 85 Parez, Ks Feng, Xs Millen, Ky Graphene Based in-Phine Micro-Sopercapcitors with High Power and Energy De sis Na Comma. 2013, 4 (Chmiola, J; Largot, Cs Tahera, P-L; Simon, P: Gogotsi, Y. Monolithic Carbide-Derived Carbon Films for: Micro Supercapacitors. Science 2010, 328 (5977), 480-483, Gao, Ws Singh, Nj Song. Ls Lin, Zs Redd, A. L. Ms Ci, E aj, Rs Zhang, Q; We, Be Ajayan, P.M, Dirt Laser Waiting ‘of Micro Supereapaciors on lyirated Graphite Oxide Films. Na. Nanotechnol 2011, 6 (8), 496-800, Futaba, D. . tal. Shape-enginerable and highly densely packed single-walled carbon nanotubes and their application as super ‘capacitor elctodes. Nat. Mater. 5, 987-994 2006) Mille. JR, Outlaw; R.A. & Holloway B.C. Graphene Double- Layer Capacitor with ac Line-Fiesing Performance. Science 320, 1637-1639 2010), Di Funtonaliaton of Graphene for int Energy Conver: sion and Storage. Acc. Chem. Res 2012, 46, 31-12 ia J; Chen, F; Li 1; Tao, N. Measurement of the Quantum ‘Capacitance of Graphene. Nat Nanotechnol. 2009, 4, 505-509 Chen, S: Zhu, J Woy Xs Han, Q5 Wang, X. Graphene Oxider MuO2 Nanowompostes for Supereapacitors ACS Nano 2010, 4, 2822-283. 2h, Vs Li Ls Zhang, Cs Casas, G; Sun, 2; Yan, 2; Ruan, Gs Pong, Z Rais AR. O.;Ktrall,C. A Seamless Thee-Dimensional Con Nanotube Graphene Hybrid Material, Na, Commun 201 3.1235, Wie, 2; Wang, X; Mao, ;Bo,2.: Kim, Cu, $ Lu, G Fen, X; Chen, J-Crampled Nitogen-Doped Graphene Nanosheets with Uitrahigh Pore Volume for High-Porformaace Supereapuctor Ad Mater. 2012, 24, 56105616, iu, CL; Chang, KHL: Hu, CC; Wen, W-C. Microwaves Asssiod Hydrothermal Syathesis of Ma3O4 Redhoed Graphene (Oxide Composites for High Powe Supeteapacios. Power Sources 2012, 217, 184192, rang, €: Pong, 2; Li, J; Zia, Ys Rawn,G; Hoang, C-C3 La, ‘Wo Hauge, R. Hs Tour. J. M. Spiting ofa Vertical Mutivaled Con Nanotaby Carpet to a Graphene Nanoribbon Cape and is ‘Use in Supeteaacitos. ACS Nano 2013, 7, SISISIS9. Lin, 1: Zhang, C Yan, Z; Zhu, Y: Peng. Zs Hauge, RH Nateson, Tou, J.M.3-Dimensonal Graphene Carbon Nant Case-Based Microspercaaciors with High Flecrechemiea Pet- formance. Nano Let. 2012, 13, 727 Ti, ZW: Pong, Fs Wang, Hos Yu Hs: Zhong, W. Xs Yang, J Phosphons?Doped Graphite Layers with High Elestrocatlti Activity forthe O2 Rediction ia an Alkaline Masi. Angew (Chem. 2011, 123, 315-3319, Yang; Yao, 7: Li Ga Fang. Gs Nie, Hs Liu, Zhou, X: Che, X.a Huang, 8. SulurDopad Graphene a an Efe Metal-Fee Cathode Catalyst for Oxygen Redocton, ACS Nano 2011, 6, 205211 Wa, ZS Winter, As Che, Ls Sum, Vs Turchanin, As Feng, X3 Millen, K. Three Dimensional Nivogen and Boron Co-Doped Graphene for High-Performance AllSoidState Supercapacitors Ads Mater 2012, 24, 513045135, Fujisawa, Ki CavzSiva, Rs Yang, KS; Kim, ¥. A Hayashi Ts Eno, My Tenones, Mj Dresselhaus, M.S Importance of Ops, etoroatom-Decorsted Elges in Chemically Doped-Grapbene for Supetcapacior Applications. J. Mater Chom. A2014, 29532930. Wu. Z, 85 Parvez, Ky Wines, As Viker, He Li, X; Han, $3 Turchanim A; Feng, X; Millen K, Layery-Layer Assembled eteonom-Dops Graphene Films wth Uhmbigh Volumetric Capci- tance and Rate Capabliy for Micro-Supetcapacitors, Ad, Matt 2014, 26, 4552-4558 Zuo, Z;' Sang. 2 Manian, A. Porous B-Doped Graphene Inspired by Fre-ce for Supeseapacitors and Mtal-Fre Catalysts, 4. Mater. Chem. A 2013, 1, [5476-16483 an, Jhang.L-L-;Lee, 8; Ob 1 Lee, KS. Potts J.J 25 ‘Zhao, X: Rul RS. Park, S. Gncraton of B-Dopa Gaghone Nanoplatelets Using a Solution Process and Their Supecapactor Applications. ACS Nano 2012, 7, 19.26. Nay LL, 2. Hong, We Sun, J; Wang. 2.; Ma, L; Wang. 1; Yan, S. Pyrlyic Synthesis of Boron-Doped Graphene and lis Applica tion as Festrode Material for Supeteapcitos. Fletoehim, Acta 2013, 108, 666-673, Lin Fs Peng. 25 Liu, Vs Ye, Rs Samuel, F. Ls Ruiz Zepeda, Fs YYcaman, MJ Yakobson,B. 1: Tour, JM. LaserIndueed Porous Graphene Fils fom Commercial Polymers. Na. Commun. 204, 5.5714 Le, . Wallan, B. M5 Byon, H. Rs Hammond, PT; Shao- Horn, Y. Nanosiicured Carbon-Based Elerodes: Bridging the Gap between Thin-Film Lithiumclon Batic and Electrochemical (Capacitors. Perey Environ. Sei. 201, 4, 1972-1988, Dong. Xs Su, C-¥s Zhang, We Zhao, 1; Ling, Qs Huang. We (Chen, Ps Ti, LJ. UlisLarge Single-Layer Graphene Obtained fiom Solution Chemical Redition and Its Electrical Proprics, Phys. Chem Chem. Phys. 2010, 12, 2164-269, Sheng, ZH; Gao, HL: Bao. W-J; Wang, B-B: Xia, X-H, Synthesis of Boron Dope Graphene for Oxypen Retion Reac- tion in Facl Cells. 3. Maer. Chem. 2012 2,390 Chea, 2; Rea, We Gao, L Lin, Bs Pei, S: Cheng, HM ‘Tce-Dimensonal Flexible and Conductive lntrconnscted Gapine Networks Grown by Chamical Vapour Deposition, Nat. Mater 2011, 10,6), 424-228, Novation of Substantive Examination Repont for Sandi Arabia Patet Application No, $163 71685, dated. Jan. 10, 2019,US 10,505,193 B2 Page 3 (56) References Cited ‘OTHER PUBLICATIONS ‘Ofce Acton for Chinese Patent Application No. 201580019802 X, dated De 20, 2018, ® cited by examinerUS. Patent Dee. 10, 2019 Sheet 1 of 63 US 10,505,193 B2 ZN 10 Expose Polymer to Laser Source ar Form Graphene from Polymer Separate Graphene from Polymer SN 14 Incorporate into Electronic Device FIG. 1AUS. Patent Dee. 10, 2019 Sheet 2 of 63 US 10,505,193 B2 20 FIG. 1BUS. Patent Dec. 10,2019 Sheet 3 of 63 US 10,505,193 B2 FIG. 1¢US. Patent Dee. 10, 2019 Sheet 4 of 63 US 10,505,193 B2 FIG. 1DUS 10,505,193 B2 Sheet 5 of 63 Dee. 10, 2019 USS. Patent - as aa “| « “a 2000 ” 2500” 3000 1500 ® (re) Aysuoyuy 1000 20 (Deg.) Raman shift (cm) FIG. 2US 10,505,193 B2 Sheet 6 of 63 Dee. 10, 2019 USS. Patent “conditions & FIG. 3US. Patent Dee. 10, 2019 Sheet 7 of 63 US 10,505,193 B2 1000 °C. Intensity (a.u.) 1000 1500 2000 2500 3000 Raman shift (cm*) FIG. 4US. Patent Dee. 10, 2019 Sheet 8 of 63 US 10,505,193 B2 a =F b oem 2 “| 2 2 g & Nis = 100° 200" 300” 400” 800 600760 860 900 282" 264" 2b6 ” 288 280” 232 Binding energy (eV) Binding energy (eV) Bae O° Intensity (a.u.) Intensity (au) ©. Nisin Pt sotaev ots int f—“ — sie” slo” sla” sla” Sle” he 386” ada ado ada ade Binding energy (eV) Binding eneray (eV) FIG. 5US. Patent Dee. 10, 2019 Sheet 9 of 63 US 10,505,193 B2 Transmittance (a.u.) 1000 2000 3000 Wavelength (cm*) FIG. 6US. Patent Dec. 10,2019 Sheet 10 of 63 US 10,505,193 B2 FIG.7US. Patent Dec. 10,2019 Sheet 11 of 63 US 10,505,193 B2 FIG. 8US 10,505,193 B2 Sheet 12 of 63 Dec. 10, 2019 USS. Patent oO | : _ | FIG. 9USS. Patent Dv(d) (em?.A*.g*.10°) Dec. 10,2019 Sheet 13 of 63 US 10,505,193 B2 an A Surface area: 342 m*.g* 36.8 A 100 1000 Pore Diameter (A) FIG. 10US. Patent Dee. 10, 2019 Sheet 14 of 63 US 10,505,193 B2 Weight Percentage (%) 100 200 300 400 500 600 700 800 900 Temperature (°C) FIG. 11US. Patent Dee. 10, 2019 Sheet 15 of 63 US 10,505,193 B2 aw be pene 3 ~ - asl — a tH} 5 5 PAS 8 L a it & d.—f\} of gat am ele Sad eo 2 m ~ oe al Re: >>90 MO is Oz 814 303842 a8 Sa a ao ae a2 ae ea (CO2 Laser Power (W) CO2 Laser Power (W) sad 3 yt poh. SL t 2 2 Te ee 2 2 (\ oe Er e ASK ie af Nd Ed \, AN tc2aw A} 30 1000 ” 1800 2000 2800” 2000 Wa a Raman shift (cm) CO: Laser Power (W) FIG. 12US. Patent Dee. 10, 2019 Sheet 16 of 63 US 10,505,193 B2 N = p Scan Rate (inch/s) 24 30 36 42 48 54 Threshold Laser Power (W) FIG. 13US. Patent Dec. 10,2019 Sheet 17 of 63 US 10,505,193 B2 FIG. 14US. Patent Dec. 10,2019 Sheet 18 of 63 US 10,505,193 B2 intensity (a.u.) OF 1900 1800 2000 2800 3000 Raman shift (em) FIG. 15US. Patent Dec. 10,2019 Sheet 19 of 63 US 10,505,193 B2 seamrate mis) Sen eh ee Cee ae TTT ae rn Tima s} FIG. 16US. Patent Dec. 10,2019 Sheet 20 of 63 US 10,505,193 B2 an =7] Os g0 eta E Gis = 4- = 40 Potential (V) CO; Laser Power (W) C04 [Scan Raters a i - = E 020. i 0.05. 00 02 04 06 08 1.0 ae 24 30 3.6 Potential (V) CO: Laser Power (W) FIG. 17US. Patent Dee. 10, 2019 Sheet 21 of 63 US 10,505,193 B2 7000- 6000+ 5000- 4000-4 z@) 3000-4 Z(Q) ae 0° 6 2 18 26 30 36 2000+ i Z (9) 10005 T T T T T 0 1000 2000 3000 4000 5000 Z'(Q) FIG. 18US. Patent Dec. 10,2019 Sheet 22 of 63 US 10,505,193 B2 ia Te TH Potentiat () Potent (¥) Sean rate (Vis) Tine (3) ines) FIG. 19US. Patent Dee. 10, 2019 Sheet 23 of 63 US 10,505,193 B2 a ‘ b i Se 4 5 : wee |e g § os = = os. y é 6 oot} oot 10 ‘do 7do0" "70800 0 700 "7a00 70000 {o(malem’) Jo(mAlcmm’) FIG. 20US. Patent Dee. 10, 2019 Sheet 24 of 63 US 10,505,193 B2 2 sigeaaies b™ Two serial devices aa a] A A ss 2 15. f\ = 08 3 1\ EB os. S 0.5 \ o é @ oz. 00 a0. : nr er er) oi 0 Time (s) Time (s) = 3 = g 3 a O28 6 8 1012 14 16 18 Time (s) FIG. 21US. Patent Dee. 10, 2019 Sheet 25 of 63 US 10,505,193 B2 bt Boos oor tes sees cur 163 0b 1 40 00 ‘ea es OM Ot Py (Wem) Pa (mW em?) FIG. 22US. Patent Dee. 10, 2019 Sheet 26 of 63 US 10,505,193 B2 aie B12 B18 meee rem nena Beet | EM go Zoe Bo Bos i Boz 5 HHS. 31 BMIM-BF. % 2000” ad00” 6000 6000 “9 1808” 3000 4800 6900 7500 can yc hunior FIG. 23US. Patent Dee. 10, 2019 Sheet 27 of 63 US 10,505,193 B2 ‘Scan raie Wed wie Sean aie Toa I(ma‘em?) geses ec 4 oa ona **IH2SO4 SS"| ° | {BMIM-BFs — 0 02 04 G8 on Wo 42 44 3 p23 Voltage (V) Potential (V) FIG. 24US. Patent Dec. 10,2019 Sheet 28 of 63 US 10,505,193 B2 Type Il (32.2°) aa FIG. 25US. Patent Dec. 10,2019 Sheet 29 of 63 US 10,505,193 B2 ee PI/H,B0, sheet BUG 2) Me with 80, 2) 80°C, vacuum,'3¢ 3) 200°C, press, Sh D+ BO, FIG. 26US 10,505,193 B2 Sheet 30 of 63 Dee. 10, 2019 USS. Patent 2 i i _ L ae | - FIG, 27US. Patent Dec. 10,2019 Sheet 31 of 63 US 10,505,193 B2 FIG. 28US. Patent Dec. 10,2019 Sheet 32 of 63 US 10,505,193 B2 FIG, 29USS. Patent Dee. 10, 2019 Sheet 33 of 63 US 10,505,193 B2 a 3s Z By ef Pf 2 i eS i 5 J\ FLY —~ ‘800 10001500 2000 25003000 30 40 50 60 Raman Shift (cm) c = S20. § | £ a0. | 5 / 8 PUHBO,) = é 40 52) 5 So, 2 0. 5 “0 "200 "460 "660" 800 ‘a00® 10 100 4000 Temperature (°C) Pore Diameter (A) FIG. 30US. Patent Dee. 10, 2019 Sheet 34 of 63 US 10,505,193 B2 . Adsorption | + Desorption | 0.0 02 04 06 08 1.0 Relative Pressure (P/P,) Adsorbed Volume (cm’/g STP) FIG. 34US. Patent Dee. 10, 2019 Sheet 35 of 63 US 10,505,193 B2 a b 3 3 & & 2 2 3 a 2 2 2 £ = = 100” abo eh a0 aio 0 «100000 aD aD 200 Binding Energy (eV) Binding Energy (eV) FIG. 32USS. Patent Dec. 10, 2019 Sheet 36 of 63 US 10,505,193 B2 2 280” 288 286 28d 202 56 «SM S82 BRO Binding Energy (eV) Binding Energy (eV) d Nis Vv 400.3 eV PUlHsBOs | 196 14120 ”CtaeSa0aS ata Binding Energy (eV) Binding Energy (eV) FIG. 33US. Patent Dec. 10,2019 Sheet 37 of 63 US 10,505,193 B2 qd, fon By a E |e z, Leo ; iw Ctra MT Ew OT TT ae Potential (), “me (s) HB Loaeing (wt) g PVA (/ Electrolyte S10 — Ss iz —1 é Silver paint Sess BIG electrodes O on Polyimide Kapton tape O41 7 70 id Current (mA/cm?) FIG, 34US. Patent Dec. 10,2019 Sheet 38 of 63 US 10,505,193 B2 = Calméiom’) © a eA 7 Dove eA" cs to 8G ea Toa Ten ao a0 SO eH Potential (V) Time (s) e fro — a at sa hes = ] roe | fae [Ea / / Tf | ees vp GAB et | Cycle Number Potential (V) Py (Wem!) FIG. 35US. Patent Dee. 10, 2019 Sheet 39 of 63 US 10,505,193 B2 8 iss b_7. E10) = 5 < ee] —& ze ? £410) 4.0 Vis g Sas, mioye) Bo} OO ae v0 02 04 08 08 10 00 02 04 08 08 10 Potential (V) Potential (V) — ol, —t9 men | 20 ekicon*) 1 mAion 8 Time (s) Time (s) FIG. 36US. Patent Dee. 10, 2019 Sheet 40 of 63 US 10,505,193 B2 = LIG-MSC ~O~ 5B-LIG-MSC 20004 £ = 2 N 10007 0 0 1000 2000 3000 Z' (ohm) FIG. 37US. Patent Dee. 10, 2019 Sheet 41 of 63 US 10,505,193 B2 ue == LIG-MSC & mee," SBLIG-MSC Ee 1 — g 0.1 s s 0.01 Ww 1 E-3 0.01 «0.1 1 10 100 Pa (mW/cm?) FIG. 38US. Patent Dec. 10,2019 Sheet 42 of 63 US 10,505,193 B2 FIG. 39US. Patent Dec. 10,2019 Sheet 43 of 63 US 10,505,193 B2 Silver paste Kapton tape FIG. 40US. Patent Dec. 10,2019 Sheet 44 of 63 US 10,505,193 B2 FIG. 44US. Patent Dee. 10, 2019 Sheet 45 of 63 US 10,505,193 B2 os) Sava sol, =002mArem| eukeee i cme § eave S087) * ~e1emates) | 02 > 6. fens = 5 oll | 2 E eal) | § 22 Bf | 5 04. © o2y | | 3 \ | ool 0. pp 0002 04 06 08 10 ‘0 280” 480” 60800 1000" 1200 Potential (V) Time {s) C die . | ae Zp renters | a i © é an | E = oo | S41 2 | 6 © a0. | | 4 20. oor 7, ‘0 ” 2000” 4000” 6000 8000 Current Density (mAicm’) Cycle Number FIG, 42US. Patent Dee. 10, 2019 Sheet 46 of 63 US 10,505,193 B2 a 2D 3 = : 3 = 3S > & Z| 2 5 a 2 2 E £ = 1000 1500 «2000 «2500 «3000 20 40 60 Raman shift (em) 20 (degree) FIG. 43US. Patent Dee. 10, 2019 Sheet 47 of 63 US 10,505,193 B2 120, S = Lis @ 100 oD 8 < 5 80 2 5 Pl o 60 ~ x= a s 404 200 400 600 800 Temperature (Degree C) FIG. 44US. Patent Dee. 10, 2019 Sheet 48 of 63 US 10,505,193 B2 a © 800. b 12 2, Fu Zou S & a : a7 gum Pr. 3 4 5 soo £ i 3? $0. 2 0. = $ 00 02 04 08 o8 10 O “o 00 “000 < Relative Pressure (P/P,) Pore Diameter (A) FIG, 45USS. Patent Dee. 10, 2019 Current (maven?) © 4 002 08 08 08 10 Potential (V) Potential (V) Sheet 49 of 63 US 10,505,193 B2 es male a 8 ee Time (s) FIG. 46US. Patent Dee. 10, 2019 Sheet 50 of 63 US 10,505,193 B2 Current malen’) Potentat Cycle Nomber FIG. 47US. Patent Dee. 10, 2019 Sheet 51 of 63 US 10,505,193 B2 a Series b para FIG. 48US. Patent Dee. 10, 2019 Sheet 52 of 63 US 10,505,193 B2 02 a b ~ & 04 thon i iE E00 z § 5 Bot |e 5 a —2ave] é aos al {NN oo 0s 10 18 20 25 30 rer er ee eT) Potential (V) Time (s) FIG. 49US. Patent Dec. 10,2019 Sheet 53 of 63 US 10,505,193 B2 current nave’) 9 Time (s} ‘Current Density FIG. 50US 10,505,193 B2 Sheet 54 of 63 USS. Patent —_ ec. 10,2019 time(s} Current (marco) Syele Number FIG. 51US. Patent Dec. 10,2019 Sheet 55 of 63 US 10,505,193 B2 8 Potent Potent) FIG. 52US. Patent Dee. 10, 2019 Sheet 56 of 63 US 10,505,193 B2 -a- MSC with PVA/H,SO, 9 SC with 1M H,SO, A” o 0 2000 ©4000 © 6000-8000 Z' (ohm) FIG. 53US. Patent Dee. 10, 2019 Sheet 57 of 63 US 10,505,193 B2 Retention (%) = So ° Nog 90 Ay ata B ag 80 70 60 50 0 2000 4000 6000 8000 Cycle Number FIG. 54US. Patent Dee. 10, 2019 Sheet 58 of 63 US 10,505,193 B2 a 1 08h + oO 8 tis 2 25 30 a5 © & 10% 20 26 0 38 40 Time (8) Time (s) FIG, 55US. Patent Dee. 10, 2019 Sheet 59 of 63 US 10,505,193 B2 2 ° Ss o be a Current (mA/cm’) ° eo 2 o 0.0 02 04 06 08 1.0 Potential (V) FIG. 56US. Patent Dee. 10, 2019 Sheet 60 of 63 US 10,505,193 B2 0.01 Li thin-ftm battery 4 V/500 pAh 1E-3 a E 16-4 LIG4ASC = in PYAIH2SO6 = Single LIG-SC = in PVAH2SO. T 165 2 w Al electrolytic capacitor Acta 3.¥1300 uF 1E-3 0.01 0.14 1 3 10 100 Py (W/cm’) FIG. 57US. Patent Dee. 10, 2019 Sheet 61 of 63 US 10,505,193 B2 —= Single LIG-SC ome LIG-MSC Ex (uWhi/cm’) 1E-3 0.01 0.1 1 10 100 P, (mWicm’) FIG, 58US 10,505,193 B2 Sheet 62 of 63 Dee. 10, 2019 USS. Patent ‘Wavelength (im) FIG. 59US 10,505,193 B2 Sheet 63 of 63 Dee. 10, 2019 USS. Patent sphonpposy 95 BD sesanos 060 osu 8 S80538 seipyms hisen soy Baan03 1009 15880. asaydsouwjye pajjosqu0d pue sase] ajqisiIA YUM OFT FIG, 60US 10,505,193 B2 1 LASER INDUCED GRAPHENE MATERIALS AND THEIR USE IN ELECTRONIC DEVICES (CROSS-REFERENCE TO RELATED APPLICATIONS. ‘This application claims priority t U.S, Provisional Pateat Application No. 61/940,772, fled on Feb. 17, 2014; and U.S. Provisional Patent Application No, 62/005. 350, filed on May 30, 2014. The entirety of each of the aforementioned applications i incorporated herein by relerence. STATEMENT REGARDING FEDERALLY ‘SPONSORED RESEARCH ‘This invention was made with government support under Grant No. PA9550-14-1-0111, awarded by the U.S. Depat- ‘ment of Defense; Grant No, FA9SS0.09-1-0581, awarded by the US. Departmeat of Defense: Grant No, FAYSS0-12-1- 0035, awarded by the US. Department of Defense; and Grant No. NOOO14-09-1-1066, awarded by the US. Depart- iment of Defense, The government has cern rights in the BACKGROUND Current methods of making graphene-based electronic ‘materials have sumerous limitation in terms of manufac- turing efficiency and electrical properties. As such, a need ‘exis for mor elective methods of making graphene-based electronic materials SUMMARY, In some embodiments, the present disclosure pertains 10 methods of producing a graphene material. In some embod ‘ments, the methods include exposing a polymer toa Taser source. In some embodiments, the exposing results in for ‘mation ofa graphene that is derived from the polymer. In some embodiments, the exposure of the polymer to a laser source also inclades a step of tuning. one or more parameters of the laser source. In some embodiments, the ‘one or more parameters include, without limitation, laser ‘wavelength, laser power, laser eneray density, laser pulse ‘width, gas environment, gas pressure, g38 flow rate, and combinations thereof. Insome embodiments, the lasee source includes, without limitation, a soi tae laser source a gas phase laser source, ‘an infrared laser source, a CO, laser souree, a UV laser source, a visible laser source, a fiber laser source, a near-field scanning optical mieroscopy laser source, and combinations thereof, In some embodiments, the laser source is a CO, laser source. In some embodiments, the polymer i inthe form of at least one of sheets, films, pellets, powders, coupons, locks, ‘monolith blocks, composites, fabricated pars, elctronie circuit substrates, and. combinations thereof. In. some embodiments, the polymer includes, without limitation, hhomopolymers, block eo-polymers, carbonized polymers, aromatic polymers, vinyl polymers, eyele polymers, polyimide (PD, polyetherimide (PED, polyether ether ketone (PEEK), and combinations thereof. In some embodiments, the polymer includes a doped polymer, such as a boron doped polymer. In some embodiments, the exposing of @ polymer to a laser source includes exposing a surface of a polymer to a laser source In some embodiments, the exposing rests in x0 ” 4s 0 © 2 formation ofthe graphene on the surface ofthe polymer. In some embodiments, the exposing inchs patterning the surface ofthe polymer with the propene. In some embod sent, the graphene becomes embeded wi the polymer In some embodiments fist surface and a second surfice of a polymer are exposed to a laser source to form graphenes on bt surfaces ofthe polymer. In some embodiments, the exposing of polymer to @ laser source results in conversion of the ete polymer to araphene.Insome embodiments, the formes graphene mate Fal consists essentially of the graphene derived from the polymer In some embodiments, the methods of the present disclosure also include a step of separating the formed graphene from the polymer to form an isolated graphene. In some embodiments, the formed graphene includes, Without limitation, singleayered graphene, multi-layered araphene, double layered prophene, pl-lyered grophene, doped araphene, porows graphene, unfunonalized ar pene, pristine graphene, functionalized graphene, tur borate graphene, graphene coated with metal nanopa cls, mt particles coated with prophene, graphene metal carbides, graphene metal oxides, graphene metal chaleo- ones, oxidized graphene, grphite, and combinations thewof. In some embodimeat, the formed. graphene includes porous graphene, In. some embodiments, the formed graphene inclides doped graphene, such os boron doped graphene. . Insome embodiments, the methods ofthe present isch sure also include a step of incorporating the graphene miter or the isolated graphene into an electronic device. 1m some embodiment, the eleewonic device isan enersy storage device or an energy generation devie, such a8 a super capacitor or a mcr supercapacitr In some embod ments, the grphene is utlzed as an elestrde in the electric device. In some embodiments the graphene is uilized a a current collector in te elecronc device. In Some embodiments the graphene ulized as an ative in the electonic device Additional embodiments of the present disclosure pertain tothe gree materials and the isolated raphenes that are formed by the methods ofthe present disclosure. In some embodiment the prphene material incdes a polymer and a graphene detved from the polymer In some ebdimnents, the graphene i on a surface of the polymer. In some embodiment, the isolated prophene is derived from a poly- ‘eran separate from the polymer. Frter embodiments of the present disclosure pertain to electronic devioes that are formed by the methods of the present disclosure. In some embodiments, the elect device has a capacitance ranging from about 2 mFlem? to bout 1,000 mFiem. In some embodiments the capacitance of the electronic device retains at least 90% of i orginal ‘alue afer more than 10.000 eyes. In some embodiments, the elevronic device has power densities ranging rom about 5 mWicm? to about 200 mWiem*, DESCRIPTION OF THE FIGURES FIG. 1 provides schemes and illustrations related to graphene materials and isolated graphenes. FIG. 1A pro Vides a scheme of methods of making graphene materials and isolated graphenes, and incorporating the products into electronic devices. FIG. 1B provides an illustration of a formed graphene material 20. FIG, 1C provides an illustea- tion ofa farmed electronic device 30. FIG. 1D provides an illustration ofa formed electronic device 4,US 10,505,193 B2 eS FIG. 2 provides data and images relating to laser-induced ‘phene (LIG) formed from commercial polyimide (Pl) films using a CO, laser ata power of 3.6 W to write patterns FIG. 2A isa schematic of the synthesis process of LG rom PI, FIG, 2B isa scanning electron microscopy (SEM) image (of LIG pattemed ino an owl shape. The scale bar is 1 um ‘The bright contrast coresponds to L1G surrounded by the arker-colored insulating Pl substrates, FIG. 2C isan SEM image ofthe LIG film circled in FIG, 2B. The seale bar is 10 jun. The inset is the corresponding higher magnification SEM image with a scale bar of 1 ym, FIG. 2D provides a crosssectional SEM. image of the LIG film on the Pl substrate. The seale bar is 20 jm. The inset is the SEM imoge showing the porous morphology of LIG with a scale ‘oar of 1 um. FIG. 2F i a representative Raman spectrum of 4 LIG film and the staring PI film, FIG, 2F is an X-ray diction (XRD) of powdered L1G seraped from the PL film. FIG. 3 provides images of materials and equipment for production of LIG fom PI by laser seribiag. FIG. 3A. 2 provides photographs of commercial Kapton PI sheets (Jet) With a 30 cm ruler, and the laser cuting system (eight) FIGS. 3B-C provide photographs of an owl and a feiter R pattemed on PI substrates. The sale bars are S mum. Ia FIGS, 3B-C, black contrast i L1G afte exposure tothe laser, while > the lighter background corresponds to Pl. The laser power used to scribe the images was 3.6 W. FIG. 4 provides Raman specira of control samples. PI sheets were carbonized in a furnace under Ar flow of 300) scem for 3 h with the following annealing temperatures: 800" C., 1000° C. and 1500° C. Raman spectra show that these carbonized materials were glassy and amorphous carbon, FIG. § provides x-ay photoelectron spectroscopy (XPS) characterization of LIG-8.6 W films (.e., LIGs formed by ‘exposing Pl sheots to lasers powered at 36 W). FIG. SA provides XPS surveys of LIG and PI, Comparison curves show thatthe oxygen and nitrogen peaks were significantly suppressed aftr PI was converted to LIG, FIG. SB provides high resolution Cs XPS spectrum of the L1G film and Pl, showing the dominant C—C peak, The CN, C—O and (C=0 peaks from PL were greatly reduced in the Cls XPS spectrum of LIG, which indicates that LIG was primarily ?. 5C provides high resolution Ols XPS. -3.6 W film and PL After laser conversion, the C—O ($33.2 eV) peak becomes more dominant than C=0 (531.8 eV). FIG. SD provides high resolution Nis XPS spectrum of a LIG-3.6 W film and PI, The intensity of the N1s peak was greatly reduced after laser exposure FIG. 6 provides Fourier transfonm infrared (FTIR) spect ‘of LIG-3.6 W and Pl fils. FTIR specira of PI show distinct ‘peaks at 1090-1776 cm", corresponding tothe well-defined stretching and bending modes of the C—O, C—N, and C=C bonds, After the laser scribing, a broad absorption from 1000 em" to 1700 em” shows that the laser seribing leads to lange vaiation in the local environment FIG. 7 provides a transmission electron microscopy (TEM) characterization of L1G-3.6 W flakes. FIG. 7A, provides a TEM image of a thin LIG lake atop a carbon ‘rid. The scale bar is 200 nm. FIG. 7B provides a TEM image of a thick LIG flake showing enfangled tree-like ripples. Th scale bar is 100 nm. Inset isthe high resolution ‘TEM (HRTEM) image ofthe yellow-circed region showing the mesoporous siructures. The seale bar is 5 nm. FIGS. TCD provide TEM images of LIG in bright and dak field view. The scale bar is 10 nm. In dark fcld view, folded ‘graphene containing several pores between § to 10 nm can ” 4 be seen. These pores indicated in arows in FIG. 7D result from curvature o the graphene ayers ined by abundant Pentagon-heptagon pairs FIG. 8 provides TEM images of L1G obtained with a laser power of 3.6 W. FIG. 84 provides an HRTEM image taken at the edge ofa LIG fake showing few-layer features and highly wrinkled structures The scale bar is 10:nm, FIG, 8B provides an HRTEM image of LIG. The seale ber is 5 nm, Average latice space of ~3.4 A comesponds to the (02) planes of graphite materials. FIG. 8C provides a Cs-cor- rection scaaing TEM (STEM) image taken a the edge of 8 LIG flake. The scale bar is 2m. The image shows an ula polyeystalline ature with gaia boundaries. FIG. 8D provides a TEM image of selected area indicated as a rectangle in FIG. 8C. It shows a heptagon with two penta sons a5 well as @ hexagon, The scale bar is 5 A. FIG. 9 provides a TEM characterization of LIG3.6 W flakes using filtering techniques. FIG. 9 provides a beght- field TEM image ofthe studied area. The seal bars S am. IG. 98 provides ist fourier wansform (FT) image ofthe L1G sample. The area has two distin parts that canbe seen onthe indexed dtractogram FFT wit the hexagonal erystal structure of carbon with Intice parameters 2-2.461 A and ©6708 A. The outer cirle spas are reflections ofthe ype (100) or (110), coresponding 10 the basal plane of sraphite 00.1. The layers are, however, very disordered and produce a rolational pater with d-spacing of 2.10 A. The ner cree spots are type (00.2), cartesponing toa d-spac~ ing of 3.35 A of the folded layers of graphene containing the cavities. FIG. 9C shows that the FFT iter uses the inner circle of type (00.2) spots and neglects the outer ciecle of type (100) spots, FIG. 9D provides careespaning fered jinages trom FIG. $C. The scale bar is $ nm. The folded sraptene structure was enhanced, FIG, 9E shows thatthe FFT filter uses the outer circle of type (10.0) spots and neglects the inner circle of type (00.2) spots, FIG. 9F shows a coresponding filtered image from FIG, 9: The sale bar js S nm. The disordered praphene stucture was enhanced FIG. 10 provides « BET spocfc surface area of LIG3.6 W. The surtace are ofthis Sample was ~342 me", Pore sizes ae distributed a 236 am, 368 am, 537 nm and 8.94 FIG. 1 provides thernogravimeti analysis (IGA) char- acterzations of LIG-3.6 W, PL and graphene oxide (GO) in ‘argon, Compared to GO, wich significantly decomposes at ~100° C, L1G is stable at >900° CPI starts to dacampose at 550°C FIG. 12 provides charcterzations of LIG prepared with ditlret laser powers. FIG, 12A provides atomic percentages of carbon, oxygen and nitrogen asa function of laser power. These values ar obaind irom high-resolution XPS. The threshold power is 24 W, at which conversion from PL to LIG oceurs. FIG. 128 provides corelations ofthe sheet resistance and LIG film thicknesses with laser powers, FIG. 12C provides Raman spectra of LIG films obtained with itlreat laser powers, FIG, 2D provides statistical analysis of ratios of G and D peak intenstios (upper panel), and average domain size along taxis (1, a. fnetion of haser power (x axis) calculated using eq 4 FIG. 13 provides a comelation of threshold laser power to sean rate, The threshold power shows a linear dependence on the seam rate. Conditions indicated by the shaded area lead to laser-based graphene-induction FIG. 14 provides characerizatons of backsies of LIG fins. HG. 148 provides a scheme ofthe baeksides of LIG films pocled from Pl substrates. FIGS. 14B-D provide SEM. dnnages of backside ofLIG fils obtained at laser powers ofUS 10,505,193 B2 5 24 W (FIG. 14B); 3.6 W (FIG. 140); and 4.8 W (FIG. 14D) All of the scale bars are 10 um. The images show increased pore size as the laser power was increased FIG. 18 provides characterization of LIG from differeat polymers. FIG. 154 provides » photograph of pattems 5 indoced by lasers on different polymers (PI, PEI and PET) ata laser power of 3.0 W. The two polymers that blackened ‘were Pl and PEL. FG. 18B provides a Raman specteum of PEL-derived L1G obtained with a laser power of 3.0 W. FIG. 16 provides electrochemical performances of LIG- _mierosupercapacitor(LIG-MSC) devices from LIG-48 W in 1 MH,SO, with their GB-indoced propesties. FIG. 164 is a digital photograph of LIG-MSCs with 12 interdigital electrodes. The scale bar is 1 mm. FIG. 16B provides an SEM image of L1G electrodes. The scale bars 200 ym, FIG. 16C is schematic diagram of LIG-MSCs device archtec- ture. FIGS. 16D-E provide CV curves of LIG-MSCs at scan rates fom 20 t0 10,000 mvs", FIG. 16F provides specific arwal capacitance (C,) calculated from CV curves as function of sean rates. FIGS, 16G-H provide CC curves of LIG-MSCs at discharge curret densities (Ip) varied fron 02 to 25 mAvem’*, FIG. 161 provides C,ealelated from CC curves vs. Ip. FIGS. 161-K provide charge density distribution ofthe states within a voltage window (-0.1,0.1) 25 ‘V for ype I and II polycrystalline shets. The defects at the ‘gain boundaries are shadowed, and numbers show the misorientation angle between the grains. FIG. 16L, provides «a carbon layer fully composed of pentagons and heptagons (pentaheptite). FIG. 16N provides calculated quantum ‘capacitance (defined in Example 1) of perfect and polyerys- talline!disordered graphene layers TIG. 17 provides elevtrochemical charocterizations of LIG-MSCs obiained fom Pl and PEL using different laser powers in 1M H,SO,. FIG. 174 is a comparison of CV ‘curves of LIG-MSCs obtained from PI ot scan rates of 100 V's"! FIG. 17B provides a specific awl capacitances of LIG-MSCs obtained from PI, calculated from CC curves at current densities of 0.2 mAvem”, as a funetion of the laser power FIG. 17C provides a comparison of CV curves of «0 LIG-MSCs obtained from PEI at scan rates of 1 Vs". FIG. 47D provides spevfic areal capacitances of LIG-MSCs ‘obiained from PEI, calculated from CC curves a a cureat density of 0.2 mAvem, asa function of the laser power. ‘Compared to PEI derived LIG-MSCs, LIG-MSCs obtained from PI have ~10x higher eapseitances prepared at the same lasce powers. FIG. 18 provides impedance spectroscopy of LIG-MSCs obiained from PL using a laser power of 48 Win | M H,S0,, Equivalent series resistance is as low as 72 obtained ata high frequency range. HIG. 19 provides electrochemical chareterizations of LIG-MSCsabiained with laser power of 4.8 W in BMIM- BF, FIGS. 194-B provide CV curves of LIG-MSCé at sean rates fom 20 mV's to 5 V's", FIG. 19C provides specific arwal capacitances vs, scan rates. FIGS, I9D-E provide CC curves of LIG-MSCs at cischarge curent densities from 0. mA/om? to 7 mAlem. The voltage drop is shown grephi cally in FIG, 19E, FIG, 19F shows a specific areal capac: tances vs. discharge curent densities FIG. 20 provides a comparison of volumetic capac tances tha ae calculated fom CC curves of LIG-MSCS in aqueous electrolyte and ionic liquid (IL). FIG. 204 provides specific volumetic capacitances asa function of discharge current deastes in 1 M 1,80,. FIG. 20B provides specific ‘volumetric capacitances as a function of discharge curent deosities in BMIM-BF,, x0 4s 0 © 6 FIG. 21 provides electrochemical performance of LIG- MSCs. in seriesfparllel combinations. Eleetolyte for doviees in FIGS. 218:B is 1 M 1,804, and for dovies in FIG. 21C is BMIM-BE,, FIG. 218 provides CC curves of two faders LIG-MSCs connected in series wih the same discharge curent density of 1 mAlem?, The operation potential window is doubled in serial configuration. FIG. 2UB provides CC cunves of two tandem LIG-MSCS in parole assembly withthe same discharge curent density of 1 mAlem?. In this configuration, capacitance is almost doubled, FIG. 21C provides CC curves of single LIG-MSCs and 10 parallel LIG.MSCS at discharge cueent densities of 1 mAfem? and 10 mAém*, respectively. Curent density inreases by a factor of 10 with 10 parallel single devies. Insets a lighted LED powered by 10 pallet LIG-MSCs, FIG. 22 provides comparison Ragone plats of dllerent coeray storage devices. FIG. 22A provides a speciticvolu- metic enemy and power densities of energy storage devies. FIG. 228 proves a specific aca encray and power densities of LIG-MSCs and LSG-MSCs. LSG, battery and Al clectolytic capacitor data were reproduced from the litera- ture for comparison. FIG. 28 provides capacity retention of LIG-MSCs con structed with LIG-48 W in 1 M H,S0, and ionic ligid (BMIM-BF,), FIG. 284 shows that capacitance, caleulated fiom CV eaves at sean rate of 100 V's", increases to 114% of the original value afer 2750 cycles, and then retains almost the same value after 9000 cycles, FIG. 238, shows tht eapocitance, calculate from CV curves at Scan rate of100 mvs, degrades to 95.5% of orginal value fier 1000 eles, and then sailzs at 93.5% after TOOD cycles FIG, 24 provides CV curves of LIG-MSCs obiained with taser power of 48 W in IM H,SO, (FIG. 244) and BMIM- BE, (FIG. 248), The curves were obtained at a sweep rate of 100 mV°s" after every 1000 cycles, FIG. 25 provides atomic structures of the calculated polycrystalline graphene shets. The aerows indicate the nit cell, and the grain boundary regions are shaded. Numbers show two types of misorientation angles (218° and 322°) betveen grins FIG, 26 provides data and images eating to the formation of boron-doped LIG (B-LIG) an fabrication of MSCs containing the BLIGs (B-LIG-MSC), FIG, 264 provides a synthetic scheme forthe preparation of BIG and fbrica- tion ofthe B-LIG-MSC. FIG. 26B provides a scheme of the dehydration reaction from PAA to a P film during curing proces, FIG. 26C provides SEM images of SBHLIG. The Inset in FIG, 26C) is the cross sectional SEM image of SB-LIG on a Pl sheet. FIG. 26D shows a TEM image of SB-LIG, FIG. 268 shows an HRTEM image of $B-L1G. IG. 27 is shows photographs ofa PAA solution wih S wt 9% of HBO, (FIG. 27A) and patemed B-LIG on the PVHBO, sheet after laser indvetion (FIG. 278) FIG. 28 shows SEM images of LIG materials with dif ferent boron losings, including OB-LIG (FIG. 284), 1B-L1G (FIG. 288), 28-11G (FIG. 280), and SB-LIG (FIG. 28D), FIG. 29 provides TEM and HRTEM imoges of LIG rmaterials with different boron loadings, inching OB-LIG (IGS. 294 and 298), IBLLIG (FIGS. 298 and 29F), 2B-LIG (FIGS. 29C and 296), and $B-L1G (FIGS. 29D and 2, FIG. 30 provides data relating to the characterization of $B-LIG materials. FIG. 3 shows the Raman spectrom of SB-LIG. FIG. 308 shows the XRD pater of SBLLIG. FIG.US 10,505,193 B2 1 30C shows the TGA curve of SB-L1Gand SB-Plat $°C/nin ‘under argon. FIG. 30D shows the pore size distribution of SBLIG FIG. 1 shows the BET measurement of B-LIG materials ‘The calculated surface area is 191 ml, FIG. 32 shows XPS survey spectra for SB-PI (FIG. 32) and SB-LIG (FIG, 328), FIG. 33 shows XPS specra of SB-L1G and PUH,BO, sheets, HIG. 334 shows the Cs specrum. FIG, 33B shows the Os spectrum. FIG. 33C shows the Bis spectrum. FIG [39D shows the Nis specu. FIG. 34 provides an electrochemical performance com- porion of LIG-MSCs with dfferet 11,80, loadings. FG. $A provides a schematic of a BLLIG-MSC device and the ‘ial photograph of flly-fabricated devie under bending. FIG, 343 provides CV curves of MSCs from Pl derived L1G, PAA derived L1G and PAA/HBO, derived LIG at sean rate of 0.1 Vis. FIG. 34C provides CC curves of MSCS fiom PI derived LiG and PAVHBO, derived LIG at a curent density of 1.0 mAlem*. FIG. MD provides CV curves of LIG-MSC and B-LIG-MSC with diferent HBO, Toadiags. The sean rate is set at 0.1 Vis. FIG. 34. provides Galvanostatie CC curves of LIG-MSC and B-LIG-MSC with diffrent 0, loadings. The eure density i set at 1 mAlem* FIG. 4° provides comparison of calculated, 2 from LIG-MSC and B-LIG-MSC with diferent H,BO, loadings. The current density is at 1 mA/em*. FIG. 4G. provides chart of LIG-MSC capacitance as a function of ‘current, An expanded schematic of FIG, 34, is also pro- Vided FIG. 38 provides data relating to the electrochemical performance of SB-LIG-MSC. PIG. 38 shows CV curves Of SB-LIG-MSC at sean rates of 10, 20, $O and 100 mV FIG. 3$B shows galvanostatie CC curves of SB-LIG-MSC at curent densities of 0.1, 0.2 and 0.5 milem?. FIG. 38C shows specific C, of SB-LIG-MSC calculated from CC ‘curves a8 a function of current density. FIG. 38D shows ceycability testing of SB-LIG-MSC. The charge-disc cycles are performed at a current density of 10 mAVem?. FIG. 388 shows a digital photograph ofa beat SB-LIG-MSC ata bending radius of 10 mm, FIG, 38F shows capacitance retention of SB-LIG-MSC at different bending radii. FIG. 35G shows bent eyclablity testing of flexible SB-LIG-MSC ato fixed bending radius of ~10 mm. The C, is calculated fiom discharge runtime at a current density of 1.0 mAlem*, FIG. 38H shows CV curves ofthe SB-LIG-MSC at different bending cycles in FIG, 38G) at a sean rate of $0 mVis. FIG. 351 shows volumetric Ragone plot of SB-LIG-MSC and Lig-Msc. FIG, 36 provides additional electrochemical performance ‘of SB-LIG-MSC. FIG. 36A provides CV curves of SB-LIG- MSC at scan rates of 0.2, 05, 1.0 and 20 Vis. FIG. 368. provides CV curves of SB-LIG-MSC at Sean rates of, 10, 1S and 20 Vis, FIG. 36C provides galvanostatie CC curves of SB-LIG-MSC at current densities of 1.0, 2.0 and 5.0 ‘mAlem?, FIG, 36D provides galvanostatic CC curves of SB-LIG-MSC at current densitios of 10, 20 and 30 mA/em* FIG. 37 provides impedance performances of LIG-MSC and SB-LIG-MSC. The testing frequency is ranging from 10° Hz to 001 Fz. This typical Nyquist plot shows a small semicircle for both devices at a high frequency region, ccomesponding (0 a fast jonie transport and low external resistance of devices. At the lower frequency region, the [Nyquist plot exhibits a linear part resulting fom the iner- face between te electrolyte and the electrode, This interiace resulls in intemal resistance of doviees. From this Nyquist, plot, Applicants can see that SB-LIG-MSC hus both smaller x0 8 external and intemal resistances than LIG-MSC. These results indicate faster ionic transport and better electrode electrolyte interface in SB-LIG-MSC. IG. 38 provides an areal Ragone plot of SP-LIG-MSC a LIG-MSC, FIG. 39 provides data and illustrations relating to the fabrication and characterization of LIG super capacitors (LIG-SCs). FIG. 39s a schematie iusiration showing the Iabrication process for assembling a single LIG-SC and sacked LIG-SC. FIG. 39B is an optical image of a fully assembled single LIG-SC manually beat. FIG. 39C is a cross-sectional SEM image ofa PI substrate with both sides laser induced 1 form graphene. FIG. 39D is an SEM image ofthe LIG films showing a porous 3D network, FIG. 39F is, TEM image of & L1G thin film showing nano-sized ‘wrinkles and ripples The inset is a HRTEM image of a LIG rnanosheet showing numerows graphene edges FIG, 40 is a photograph ofa hal-side LIG electode for LIGSCs. FIG, 41 is an illustration ofthe fabrication process of a solid-state LIG-MSC. FIG. 42 provides data relating to an electrochemical performance of a single LIG-SC. FIG. 42A provides CV curves of L1G-SCs at sean rates of S, 10, 20 and 50 mV. FIG. 428 provides Galvanostatic CC curves of LIG-8Cs at ccurent densities of 0.02, 0.05, 0.10 and 0.20 mAlem®. FIG. 42C pravides specific areal capacitances calculated from CC curves as a function of current density. FIG. 42D provides cyelability testing of LIG-SCs with a CC current deasity of 08 mAvem* FIG, 43 provides data relating to the characterization of LIGs. FIG, 434 provides « Raman spectrum of LIGs. FIG. 4438 provides an XRD spectrum of LIGs, FIG, 44 provides a TGA plot of LIG and PI substetes under angoa. PI strts to decompose at ~§50°C., while LIG remains stable up to 900° C. The L1G for this analysis was removed from the underlying PI film as described in the Methods. FIG, 48 provides a BET measurement of L1Gs, FIG. 45, provides nitrogen adsorption/desorption curves of L1Gs. The calculated surface area i 330 mg FIG. 48B provides pore size distributions of LIGs. IG, 46 provides additional electrochemical performance of a flat, single LIG-SC. FIG. 464 provides CV curves of LIG-SCS at sean rates of 01, 0.2, 05 and 1.0 Vis, FIG. 468, provides Galvanostatic CC curves of LIG-SCs at curent densities of 05, 1.0 and 2.0 mAlem*. FIG, 47 provides electrochemical performance of LIG- SSCs under bending. FIG. 4TA provides CV curves of LIG- SSC at varying bending radi. The scan rate was 0.02 Vis, FIG. 47B provides capacity retention at different bending radius, Capacitance retention was calculated trom CC curves at a current density of 005 mA‘em*. FIG. 47C provides eyclability testing of flexible LIG-SCs, Capaci- tance retention was calculated from CC curves ata curent ensity of 04 mAlem*, FIG. 48 provides ‘electrochemical performances of stacked LIG-SC¢ in series and parallel citeuts. FIG. 48, provides an illustration of a stacked series LIG-SC and its corresponding circuit diagram. FIG. 4¥B provides an illustration of a stacked parallel LIG-SC and its corresponding circuit diagram. FIG. 48C provides galvanostaie CC curves comparing a single LIG-SC to a stacked series LIG-SC ata ccurent density of 0.5 mA‘em’. FIG. 48D provides galvanostatic CC curves comparing a single LIG-SC toa stacked paralol LIG-SC at a current density of 05 mAlem®. FIG. 4 provides a eyclabilty testing ofa flexible stacked seriesUS 10,505,193 B2 L LIG-SC ata current density of 0.5 mAfem*. Inset shows the initial CV curves (black) and the 4000 CV curve (rod) at ‘a scan rte of 0.1 Vis. FIG. 48F shows a eyelbility testing ‘of a lexble, stacked parallel LIG-SC ata current density of 1.0 mAlem, Inset shows the initial CV eurves (black) and 5 the 6000" CV curve (red) at a sean rate of 01 Vis FIG. 49 provides electrochemical perfomances of stacked LIG-SCs in series configurations. FIG. 49A provides CV curves of series LIG-SCs at sean rates of 5,10, 20 and 50 mV/s. FIG. 49B provides galvanostatic charge-discharge ‘curves of series LIG-SCs at current densities of 0.1,02 and 05 mA‘em* FIG. 50 provides electrochemical performance of stacked LIGSCs in parallel. FIG. S04 provides CV curves of parallel LIG-SCs at sean rate of 10, 20, $0 and 100 mVis. FIG. 50B provides galvanostatic charge-discharge curves of parallel LIG-SCs at eureat densities of 0.1.02, 0.5 and 1.0 mAiem*. FIG. S0C provides specific areal capacitance cal~ culated from discharge runtime as a function of current density. FIG. 81 provides electrochemical performances of LIG- MSC devices. FIG. 51A provides an illustration ofa flexible LIG-MSC. The inset e a photograph of a LIG-MSC fixed a 1 bending radius of 12 mm, FIG, SIB provides CV curves 2s ‘of LIG-MSCs at scan rates of 10,20, 0 and 100 mis. FIG. SIC provides Galvanostatic CC curves of LIG-MSCs at ccurent densities of 0.1, 0.2, 0.5 and 0 mA/em. FIG. 51D provides specific C, of LIG-MSCs from aqueous 1M H,SO, and PVA/H,SO, calculated from CC eurves as a function of the cureat density, FIG. SIE provides capacity retention of LIG-MSC at different bending radii, Capac tance retention was caleulated from CC curves at current density of 05 mAlem. FIG. SIF provides eyclability testing of flexible LIG-MSCs. Capacitance reteation was cileuated from CC curves ata current density of 0.5 mA/ent FIG. 82 provides additional data relating to the electrochemical performance of at LIG-MSC devices. FIG. 524 provides CV curves of LIG-MSCs at sean rates of 0.2, 05, 1.0 and 2.0 V/s. FIG. 528 provides CV curves of LIG-MSCs at scan rates of 50, 10 and 20 Vis, FIG. $2C provides CC ‘curves of LIG-MSCs at cunent densities of 2, 5, 10 and 20 Alem’ FIG. 3 provides impedance performances of LIG-MSCs with aqueous 1 M H,S0, and PVAJH,SO, electrolyte, This typical Nyquist plot shows a small semicircle at a high frequency region that comespoads to the ionic transport which contributes to the extemal resistance of the device. ‘The lower frequency region of the Nyquist plot exhibits linearity due tothe interaction between the electrolyte and electrode. This interface results in internal resistance of the device. From this Nyquist plot, Applicants can see that LIG-MSC in PVAVH,SO, has both a smaller external and intemal resistance tan those in agueous H,S0,. These results indicate faster ionic transport and better electrode clectolyt interface in LIG-MSCs using PVAVH,SO, FIG. $4 provides data relating to the eyelabilty test of LIG-MSCs. The CC current density was set at 1.0 mer ‘The capacitance remained >XP% after 8000 cycles. FIG. 58 provides electrochemical performance of LIG- MSCS in series or parallel combinations. FIG, $5A provides, CC curves of two tandem LIG-MSCs connected in series with the same discharge current density. The operation potential window is doubled in series configuration. FIG. ‘351 provides CC curves of two tandem LIG-MSCs in paral] assembly withthe same discharge eurent density. In this coafiguration capacitance is almost doubled. Both tan- x0 ” 4s 0 © 10 dem devices and the single device were applied with the same dischargeicharge current density FIG, 86 provides CV curves ofthe flexible LIG-MSC at iffereat bending radius, The sean rate is set at 0.1 Vis. FIG, 87 provides Ragone plots of single LIG-SC, LIG- MSC and commercial enerpy storage devices. FIG, 88 provides Ragone plots of single LIG-SC and LIG-MSC in specific areal energy and power densities, FIG. 89 provides an absorption spectrum ofa polyimide film. The four vertical lines represent where a tunable CO; laser could specifically address key lines of polymer absorbance o induce graphene formation, FIG, 60s. drawing showing the use of visible lasers and ‘an option of coupling ato controlled atmosphere chamber with an optical fiber. DETAILED DESCRIPTION Its t be understood that ott the foregoing general description and the following detailed description az illus teative and explanatory, and ae nt restrictive ofthe subject ter a claimed, la this application, te use ofthe singular includes the plural, the word “a or “an” means “at least one", and th use of “or means “andor unless specially stated otherwise. Furthermore, the use ofthe term “includ ing”, as well as other forms, such as “includes” and “included s wot iting. Als, temas such 2s “element or “component” encompass both elements or components com- prising one unit and elements or components that comprise more than one unit unless specifically stated other “The section headings used herein are for organizational purposes ancl ae nt tobe conse as limiting the subject, muller described. All documents, o portions cf documents, cited in this application, including, but not limited wo, lens, patent applications, articles, books, and wetises, ae hereby expres incorporated herein by reference in their eatireyforany purpose. Inthe event that one or mor ofthe Jncorporated iterate and similar materials defines a teem ina manner that contacts the definition of that tem in this application, this application coatos. Over the past decade, graphene based nanomaterials have boen widely studied due to their unique physica and chemical properties. Through synthesis and engineering desiu, graphene can have porous and 3-dimensional (3D) sruc- tures, leading toa wide range of applications from compos it fillers to energy storage devices. Despite the tremendous advances, cuneat synthesis methods of porous graphene require ether high temperature procesing or multi-stepped chemical synthesis routes, thereby lessening theie wide- spread commercial potenal, Therefore, straightforward synthesis, and especially atteming, of graphene based nanomaterials ina scalable approach is stil a technologi- cally important» goal in achieving commercialized microscale energy storage deviees. Tor insane, glassy carbon has been produced from jnsulting polyimide via pulsed ultraviolet (UV) lsc reat- ment. However, to Applicants’ knowledge, the detailed sirdctural study’ of the obtained materials, especially at the nearatomic level the corelation ofthe materials’ structures 10 their eletrochemial performances; and the formation of araphene by this route have not been disclosed “Moreover, the tehnige of laser sribing insulating poly- rer for the fabrication of eletronic devices (eg, eneray storage devices, such as micosupereapecins or MSCS) hes sot yet been demonstrated. In fact, the coselective sya thesis and ptteming of carbon nanomaterials fo incorpo ration into eletronie devices has heen a challengeUS 10,505,193 B2 un Energy siorage systems, such as supereapocitors (SCS) ‘and hin ion batteries (LBs), have beea widely’ stud ‘over the past few years inorder to meet the pil growing demand for highly elcient energy devices, Intense ongoing research has focused on miniaturized potable electronics Which require small size, ight weight and mechanical ex- ibility while maintaining high enerey and power densities. Recent progress. in. mierofabrieation technologies has allowed for the in-plane manulacturing of microsupercapacitors (MSCs) made using lithographic technigues that would be suitable for integrated cites. However, such fabrication methods may not be east- some embodiments, the laser sourees ofthe present disco sure have power tanges that can vary based upon the absorbance of the polymer ata chosen laser wavelength. ‘The laser sources ofthe present disclosure can also have various pulse widths. For insanee, in some embodiment, the laser sources ofthe present disclosure have pulse widths that are in the range of femtoseconds, nanoseconds, o ‘milliseconds. In some embodiments the laser sources of the present disclosure have pulse widths that range from about 1 femtosecond to about 1 ms. In some embodiments, the laser sources of the preset disclosnre have pulse wits that range from about 1 femtosecond to about 1 ns. In some ‘embodiments, the ler sources of the present disclosure have pulse widths that range from about J ys to about 1 ms. In some embodiments, the laser sources of the present dlisclosure have pulse widths that range from about 1 ys to ‘bout 100 is, In some embodiments, the laser sources of the present disclosure ave pulse widths that range fom about 10s to about $0 ps. In some embodiments, the laser sources of the present disclosure have pulse widths of about 15 ys. Additional pulse widths can also be envisioned, In some embodiments, the laser source is a CO, laser source with a wavelength of about 10.6 um. As set forth in ‘moze detail in the Examples herein, Applicants have ‘observed that the application of CO; laser sources to poly mer surfaces (e.2, polyimides) at wavelengths of about 10.6, um provides porous graphenes with optimal electrical properties. ‘The use of additional laser sources at different wavelengths can also be envisioned. For instance, in some ‘embodiments the polymers ofthe present disclosure may be ‘exposed toa single laser source. In some embodiments, the polymers ofthe present disclosure may be exposed to 1Wo or more laser sources, In some embodiments, the polymers of the present disclosure may be simultaneously exposed 0 tww0 or more laser sources, In some embodiments, the two or more laser sources may have the same or dlerent wave lengths, power ranges, and pulse widths. Exposure of a Polymer t a Laser Source ‘Various methods may be uilized to expose polymers toa laser souree. In some embodiments, the exposure occurs ‘manually. In some embodimeats, the exposure oceurs auto- 4s 14 ‘matically For instance, in some embodiments, the exposure ‘ceurs automatically through computer-contolied mecha- nisms. In some embodiments, the exposure occurs automatically through @ computer patterning system. In. some embodiments, the exposure occurs automatically through aulomiated processing fines. In some embodiments, the exposure occurs automatically through automated processing lines with multiple laser sources. In some embodiments, the mmhtple laser sources could vary in wavelength or power to cause different degrees of graphene formation over diferent regions ofthe polymer, In some embodiments, the exposure of polymers toa laser source includes pulsed laser irradiation, In some embod iments, the exposure of polymers to laser source includes continuous laser imadiation. In some embodiments, the exposure of polymers to a laser source includes patterning a surface of the polymer with the formed graphene. For instance, in some embodiments, the surface of the polymer is pattemed into interdigitated shape. In some embodiments, the exposure of a polymer to a laser source includes a sep of tuning one or more parameters of the laser source. In some embodiments, the one or more tunable parameters of the laser source include, without Timitation, laser wavelength, laser power, laser energy density laser pulse widths, gas environment, 2s pressure, gas flow rate, and combinations thereof. In some embodiments, the one or more parameters of laser source are tuned aecording to one or mare atibutes of the exposed polymer. In some embodiments the one or more atibutes of the exposed polymer include, without fimita- tion, polymer type, polymer thickness, polymer moephol- ‘ogy, polymer stricture, polymer absorbance spectrum, a substrate upon which a polymer may be allied, and combinations thereof. In some embodiments, the one or more parameters of a laser source are tuned in order to maximize the absorption of the laser wavelength by the polymer. For instance, in some embodiments, the laser wavelength of the laser source is tunod to match an absorbance band of a polymer. In some embodiments such tuning optimizes lser light absorbance by the polymer and resulls in optimal graphene fomation upon lase-polymer interaction. In some embodiments, the absorbance andl of the polymer corresponds to the wave- Tength of the laser source In some embodiments, the one or more parameters of laser souree are tuned in order to contol the penetration depth of the laser wavelength by the polymer. In some embodiments, the penetration depth (or absorption depth) of laser source is maximized by tuning the wavelength ofthe laser source, As such, in some embodiments, a strongly sorbed wavelength canbe focused on a polymer surface to create desired form of graphene, Moreover, he availability {0 choose from many wavelengths can allow for selection of ‘wide range of penetration depths into a polymer or ype of polymer by changing the wavelength of the laser source. ‘This in turn allows for controlling the depth of the foemes graphene and the type of polymer from which graphene can be formed. For instance, in some embodiments, the laser source can be tuned to create a narrow and shallow line of sraphene on a surface ofa polymer by using a well-focused laser at lower power rang. In some embodiments, the exposure of a polymer 10 a laser source includes a step of tuning one or more parameters of the polymer. For instance, in some embodiments, a polymer’s absorbance band can be tuned to match the ‘excitation wavelength of a laser source. In some embod mens, the tuniag occurs by modifying the structure oftheUS 10,505,193 B2 15 polymer. In some embodiments, the modification ean ensure ‘optimal graphene formation upon laser-polymer interaction. In some embodiments, the absorbance hand of a polymer ‘ean be modified to match the excitation wavelength of the laser source by adding @ compound to the polymer that absorbs wel athe excitation wavelength ofthe laser source. In some embodiments, the exposure of a polymer to a laser source can include the utilization of optical miero- scopic techniques. In some embodiments, the microscopic techniques can be used o provide nanometer-scaed pattems (of graphene on the polymer suriee. For instance, in son ‘embodiments, near-field scanning optical microscopy (NSOM) can be used during the exposure of a surface of a polymer to laser source to provide nanometer-scaled pattems of graphene on the polymer surface. In some ‘embodiments the nanometer-scale pattems of graphene on the polymer surface can have resolutions of about 20 am. Polymers ‘The laser sourees ofthe present disclosure may be applied to various types of polymers. For instance, in some embodli- ments, the polymers ofthe presen disclosure inchide, with ‘out Fiitation, vinyl polymers, homopolymers, block oo- polymers, carbonized polymers, aromatic polymers, cyclic polymers, polyimide (PI), polyetherimide (PEI), polyether ether ketone (PEEK), and combinations thereof. In some ‘embodiments, the polymers ofthe present disclosure include polyimide. In some embodiments, the polymers of the present dis 1500° C, the resulting Raman spectrum is similar to that of glassy carbon (FIG, 4). However, the spectrum for L1G (FIG, 2E) is clearly diferent from tat of glassy carbon. The 2D peak of LIG canbe fitted with only one Lorentzian peak centered at 2700 em the same as in single-layer graphene (SLG), but with larger full width at half maximum (FWHM) of ~60) mi", This 2D band profile is typical of that found in 2D graphite consisting of randomly stacked graphene layers long thee axis Finally, DIG intensity ratio indicates. high degree of graphene formation in the L1G filmsUS 10,505,193 B2 25 ‘The XRD pattem (FIG. 2F) shows an intense peak centered at 20-25.50, giving an interlayer spacing (|) of 3.4 ‘Avbenween (002) planes inthe L1G. The pater indicates the high degree of graphene formation, The asymmetry of the (002) peak, with tailing at smaller 20 angles. also points to an increased |, The expanded I, can be atibuted to regions ‘where defects are distributed on hexagonal graphene layers. ‘The peak at 2-42.90 is indexed to (100) reflections which are associated with an in-plane structure. Using equations 2 ‘and 3, and the methods described in this Example, the crystalline size along the c-axis (L,) and asaxis (L,} are calenlated to be ~17 nm and ~32 am, respectively ‘The XPS spectrum of LIG-.6 W shows dominant C—C ‘peak with greatly suppressed CN, C—O and C=O peaks (FIG, 8). Such resuls suggest that L1G films are dominated by sp-carbons,agrecing well withthe Raman and XRD results. This is further confined by comparison of the distinctive FTIR spectra of Pl and LIG-3.6 W (FIG. 6). “The miro and nano-structure of L1G flakes was inves- tigated by transmission electron microscopy (TEM), FIG. ‘TA shows thin LIG flakes with few-layer features as further 2 indicated from the edges ofthe fake in FIG, BA. Moreover, ripple-tike wrinkled structures can be observed from the surface ofthe lakes. These structures in graphene have been shown 10 improve the electrochemical performance of devices. Thicker flakes exhibit mesoponous structures (FIG. 7B). High-resolution TEM (HRTEM) images in FIG. 8B revels thatthe nano-shaped ripples are exposed ges of ‘wuphene layers. The formation of these spples could be atibuted to themal expansion caused by Isr itaiation. “The average latice space of ~3.4 A. shown in FIG. 85 corresponds wo the distance between two neighboring (002) planes ia graphitic materials, and it agrees well with the XRD reslis The abonation-conected scanning trasmis- sion electron microscopy (CsSTEM) image (FIG. 8C) shows the unustalulra-polyeystaline featare of L1G Bakes ‘ith disordered grain boundaries. This observation i further depicted in FG. 8D, where a hexagon lative anda heptagon ‘with two pentagons is shown. These abundant pentagon- hheptagon pis can aecount forthe curvature of the graphene layers lading tothe porous structure (FIGS. 7C-D and 9). Theoretical caleulatons suggest that the aforementioned defects could enhance eeciochemical capacity (as dis cussed in dsal herein. IG has surface area of 340 sr by BET, wit pore sizes of less than 9 nm (FIG. 10). Thenmogravimetic analysis (TGA) measurement under argon (FIG. 1) shows thatthe decomposition temperature of PI is ~S50° C, and iG is >900° C,, while that ofthe often used graphene precursor, graphene aide (GO), is 190°C. Example 13. Effect of Laser Power ‘To investigate the effect of laser power, LIG was prepared using powers ringing ffom 24 W to 54 W in 06 W increments at a sean rate of 3.5 inches per second, In FIG. 12A (plotted from Table 1), beginning at 2.4 W, the atomic percentage of carbon sharply increases from the original 71% in PL to 97% in LIG while the atomic percentages of both nitrogen and oxygen decrease precipitously to <3%, This threshold power effect has been well-studied in UV ablation of polymers. Marin Carbon) __Oraen 4) _Niogen 09) Polyimide mS 70 4s 0 26 -continued Macinle Gabon 6) _ Owen 6H) _Nivaen 09) Liga w 77 12 TH ugaaw 13 3 03 Ugsow 58S a a 1iG36W oS “ te tiG42 W sa Ss 03 Liga W a ‘9 we lcssw 513 10 “Table 1 provides a summary of atomic pereentage of elements in raw material (PD) and L1G derived from diferent Jaser powers, All of the data were obtained by high-resolution XPS sean. ‘The threshold power shows a linear dependence on the sean rate (FIG. 13). If the sean rate increases, higher threshold power needs o be applied in order to initiate the srapitization, Meanshil, the sheet resistance (R,) of LIG- 24 W is reduced t0 35.9 1" (FIG. 2B). Below the threshold of 2.4 W, Pls an insulator with R>>90 MOC" (instrument limit) As the laser power inereases 0 5.4 W, R, is gradually reduced to @ minimum value of <15 8 C's the translated conductivity is ~25 Sm, higher than in laser. reduced GO. FIG. 128 shows two distinct slopes of Rs vs Jaser power. The slope when the laser power was <4.2 Wis larger than the one when it was >42 W. This suggests that ‘when the laser power is <42 W, the thermal power domi- rates the quality of the films. Therefore, increased laser power leads to higher graphene formation. As the thermal power rises above 4.2 W, oxidation starts to play an ineeas ingly deleterious role in the quality of the films. Therefore tne slope lessens. As expected, higher leser power tends to inerese poros- ity, as shown in the SEM images taken on the backside of the LIG films (FIG, 14) that had been pooled off the PI substrate. Raman spectroscopy isa power tool to obtain crystalline size (L,) along the a-axis of graphitic materials by analyzing ratios of the integrated intensities of G and D peaks ley). FG. 12€ shows representative Raman specra Of LIG films stained with laser powers from 2.4 to 54 W, “The statistical analysis of Tp vs. laser powers is ploted in the upper panel of FIG. 120. The L, values calculated from the average Ip ratio using eq 4 and the methods described in this Example is shown in the lower panel of FIG. 12D, showing increased Lup to ~40 amas te laser power rises {048 W. This increase can be atibuted to increased surface temperatures. Further increase in power degrades the quality of the LIG with L, of 17 nm in LIGS.4 W, which is atibutable to the partial oxidation of L1G init. This can be further verified from profound defec-comeated I peaks centered at -1620 em"? in LIG-54 W (FIG. 120). Example 1.4. Discussion Laser ablation of polymers has been studied since the carly 1980s. Because af its complex nature, the detailed mechanism is sill debated as being a photothermal or photochemical process, or both, Since photochemical pro- ‘esses tends to occur in lasers with short wavelengths and tulra-short pulse widths, Applicants’ infrared L1G fomnation is more likely to be caused by photothermal elfets due ois, Tong wavelength (10.6 ym) and relatively long pulses (14, i). The energy from laser irradiation results i lattice vibrations which could lead to extremely high localized temperatures (©2500° C.) that can be qualitatively detectedUS 10,505,193 B2 27 by laserindced fluorescence. This high temperature could easily break the CO, C=O and N--Cbonds, a8 confirmed by the dramatically decreased oxygen and nitrogen contents in LIG (FIG. 124). These atoms would be recombined and released as gases, Aromatic compounds are then rearranged 5 {form graphite structures, during which oxidation of these ‘graphitic structures can be minimized by an overlayer of the evolved gases. ‘Without being bound by theory, Applicants have found that the mechanism of laser graphtization in polymers is. 10 steongly correlated to the siutural features present in the repeat units, such as aromatic and imide repeat unit. “Attempts were made to generalize this laser induced graphi- tization process by testing 15 different polymers. Out of them, only two polymers, PI and polyetherimide) (PEI, 15 Doth of which contain aromatic and imide repeat units, can 28 orm L1G in this example (Table 2 and FIG. 18). Four other step growth polymers and all of the chain growth polymers tested did not affont LIG in this Example. The reason for other step growth polymers being inactive is not conch sively known, but sugested by the fact that at 10.6 um, the CO; laser wavelength has a strong absorbance inthe pol mide film (FIG. 59). However, use of lasers that have other wavelengths can be used to target polymers that have absorbances atthe laser wavelength line. Additionally, one could add a compound to a polymer wherein the added compound absorbs well atthe frequency of the laser used, and that additive becomes spectroscopically excited by the laser, thereby transfering its energy, thermally or photo chemically, to the polymer, eausing the polymer to form graphene. In some cases the added compound would act as a sensitizer, eee er s ry s Re 5 o l A Flint etyene popyene | FEP a NoUS 10,505,193 B2 Pi] 30 -continued ull ne Simbei ak rapitt Petrealiony alae PEN Tl Ne PRE Q Scr] Teor rire ran Ne be Polystyrene ps Xo Pojearone Pa ° xo I ome. Palyepine Pe % Polya! abel PVA Xo obo metryis) PMMA Xe Aco tude syne ABS Xo oN ‘Table 2 provides a summary of polymers, their chemical repeat units and their LIG-forming capability. Out of 15 polymers, only PI and PEI were successlully converted to LG in this example. Nonaromatic hydrocarbons undergo almost complete degradation without graphene Jomation. Seat ON ee Fa gc even asthe imide group in Pl and PEL polymers favor LIG formation. PAN films are not commercially avaible and ‘were thus prepared in-house. Though PAN is a precursor to carbon fiber, it does not form graphene well unless heated slowly to permit cyclization and N-extrusoa, © Example 1. Fabrication of LIG-MSCs Next, Applicants fabricated in-plane interdigitated LIG rmcrosupercapacitors (LIG-MSCs) in which LIG serves as both the active electrodes and the current collectors. Well= defined LIG-MSC electrodes are directly written on PI sheets with neighboring distance of 300 ym (FIGS. 16A-B). Ths distance can be further decrease by using smaller laser aperture. After Writing, silver paint was applied fon common positive and negative electrodes, and then Kapton tape was employed 10 define the active electrodes. FIG. 16C depicts the device architecture ofthe fabricated LIG-MSCs, Cycle voltammetry (CV) and galvanostateUS 10,505,193 B2 31 chargeischarge (CC) measurements were performed 0 investigate the electrochemical performance of the febr- cated LIG-MSCs, All CV curves of LIG-MSCs made with IG electrodes at various laser powers are pseudo-retan- ‘ularin shape, which indicates good double-layer capacitive behaviors (FIG. 17). LIG-MSCs consircted with LIG-48 W elecrodes generally exhibit the highest specific areal capacitance (C,) (FIG. 17B). The C, of LIG-MSCs made from PE is~10% of those from PI (FIGS. 17C-D), possibly associated with the lower nitrogen content. Therefore, all ‘other electrochemical measurements were carried out on LIG-MSCs made from Pl witha lsee power of 4.8 W. FIGS, 6D-E are the CV curves at scan rates ranging from 20 t0 10,000 ms"! Although there exist certain eves of oxygen ‘or nitrogen contents in LIG, the devices do not exhibit pseudo-capacitive behavior 38 suggested from CV curves at 2 small rate of 20 mVs", which shows no anodic and cathodic peaks. Even at high rate of 10,000 mV's", the CY curve maintains is pseudo-rectangular shape, and this is 2 suggestive of high power performance, The Casa function of sean rate is shown ia FIG, 16F, Ata scan rate of 20 mV-s"', the C, is >4 mF-em", which is comparable to or higher han the values obtained in recently reported GO- derived supereapacitors. The specific capacitance of the 2 material by weight is~120 Fx" At 10.000 mV’! the C, is sill higher than 1 mF-em“*. This optimal capacitive ‘bchavior is further confined by the nearly tiangular CC ‘curves at varying curent densities from 02 to 25 mAvem™* (FIGS. 166-1). From the C, vs. discharge curent densities (Up) plotted in FIG. 161, the LIG-MSCS can deliver C,, of 39 mF-em at lp of 62 mem? and still maintain 1.3 ‘mem, even whea the devices are operated at Ip of 25 ‘mAvenr. This value is comparable or higher than those ‘reported for some carbon-based MSC atthe same current deosities. The impedance measurement shows low equivae Teat series resistance of 19 (FIG. 18). Other than aqueous electrolyte, Applicants also explored the use ofan ionic liquid electrolyte in LIG-MSCs. FIG, 19 shows CV and CC curves of LIG-MSCS in I-butyl-3- ‘methylimidazolium teraluoroborate (BMIM-BF.), which suggest optimal capacitive behaviors. The corresponding specific volumetric capacitances (Cy) vs. discharge vol metre curent densities (Ip) is shown in FIG. 20 For practical applications requiring either higher opera tion potential or cureat or both, supercapactors eed tobe ‘connected in serial andor parallel configurations. As shown in FIG. 21, the output potentials and currents can be well controlled by serial and parallel connections to pawerlight- cemiting diodes (LEDs). Compared with commercial devives such as aluminum electrolytic capacitors (SECS), thin film Li-ion batteries, and activated carbon supercapactors (ACSCS), LIG-MSCs offer more energy or power density or both as seen from the Ragone plas (FIG. 22). When compared with rently demonstrated reduced GO- film (called MPG films) MSCs (MPG-MSCs) and laser scribed graphene MSCs (LSG-MSC8), LIG-MSCs ean deliver comparable F,, although power performance news to beenhanced. Using specific areal energies (F.,)and power (P.) densities, one can obtain reasonable values for comparing performance of in-plane MSCs intended for commer- 1 applications. FIG. 22B shows that LIG-MSCs exhibit ~100shigher E, and ~4xP, than MPG-MSCs, Furthermore, LIG-MSCs offer slightly beter Ey than LSG-MSCs with ‘comparable power performance. In addition, eyeling pefor= mance shows that there is negligible capacitance degrading after 9000 cyeles in aqueous electrolytes and 7000 eyes in ” 32 ionic liquid electrolytes (FIG. 23). Moreover, CV curves at every 1000 cycles show no involved pseudo-capactive peaks (FIG. 24), Without being bound by theory iti envisioned that the high capacitance ofthe L1G-MSC ean be atebuted tothe 3D network of highly conductive graphene showing high surface area and abundant wrinkle, which provide easy acess for the eleetrolyte to form a Helmholtz ayer. Moreover, density function theory (DFT caleulations suggest thatthe ulta-polyerstalline nature of LIG-MSC ean also improve the capacitance. The total capacitance (C) is contributed by te quantum capacitance (C,), and the ligud electro (C,) consisting of Helmholtz and diffsion regions: C=C,” C!.C, is mostly controled by surlace are. C, represents the intrinsic property ofthe electrode material ‘and can be calelated from its electronic strcture in eg 1 w one y In equation 1, $ isthe surlae area, V isthe applied voltage, Dis te density of states, ei the Femi level, and e is the electron charge. The ulir-polyerytlline nature suggest hy FIGS. C-D as wel s FIG. 12D indicate the sundance of grain boundaries (GBs), which are composed of pealagon and heptagon pais. These defects are more ‘metallic’ than regular hexagons, and therefore can he expected to enhance the charge storage performance, Cal- culations are performed by using DFT. The GB efloct is rmodeled by a planar polycrystalline graphene sheet (FG. 25), Two types of GBs are considered 3s representatives ics. 167). As another case, Applicants also consider @ graphene sheet fully composed of pentagons and heptagons (FG. 161. also refered to a a “pentaheptie"). The calculated C, is shown in FIG. 16N, Clearly. a polyerystaline sheet has & ruch higher, than perfect graphene, as resultof a higher density of stats near the Fermi level due tothe presence of Gils The type I GB enanees the storage more than in ype [.asithas higher defect density along the GBs. The highest, Cis found in pentaeptte duc to its highest disorders and alley. Though here only the C, is calculated, it ean be expected ta the C,nereasesasC,neeases. These ess suggest that GBs-rich L1G with malmained electric conductivity would be able to deliver higher capacitance than perfect defetiree graphitic materials. Chemical doping of 1s ech ulte-polyerytalline domains of pentagon-heptagon rings might further enhance the capacitance. Ths is he fist theoretical calculation that shows the effet of pentagon hepiagon gran boundaries on charge storage, a result that could inspire theoreticians to fuer explore the potential of these materials Tn summary, Applicants have demonstrated in this Example a one-step and scalable approach forthe prepari- tion of porous graphene from commercial polymer shexts using CO, laser irradiation uder ambient conditions. Appi- ants have establish that the physical and chemical prop- entes ofthe resulting LIG stuctres render them uniguely suitable for enery storage deviees delivering, promising cloctrchemical performance. The use of commercially ‘vailable polymer sheets would allow fo oll manu facturing, which can faite commerilizaton. Theoret- cal modeling suggests that the enhanced capacitance could Paatclly come from defctich boundaries ia LIGUS 10,505,193 B2 ei Example 1.7. Methods Kapton polyimide (Pl, Cat. No. 2271K3, thickness 0,005") and other polymers sheets used inthis Example were all purchased from MeMasterCarr unless stated otherwise. 5 ‘The polymers were used as ecsived unless noted otherwise Laser scribing on polymer sheets were conducted with a carbon dioxide (CO,) laser eutter system (Universal X-660 laser cutter platform): 10.6 jm wavelength of laser with pulse duration of ~14 ys, The beam size is ~120 um. Laser power was varied from 2.4 W to 5.4 W with increments of (046 W. The laser system offers an option of coatelling the sean rates ftom 0.7 to 23.1 inches per second. The laser system also provides an option of setting pulses per inch (ppi with range fom 10 to 1000 ppi. By experimentation it was discovered that the ppi rate played litte role in changing the threshold power. Other than as specifically Stated, the same scan rate of 3.5 inchs snd 1000 ppi were used for all experiments, All ofthe laser experimenis were 2 performed under ambient condition. Example 1.8. Device Fabrication IG electrodes were directly written using the computer- 28 controlled CO, laser. In the MSCS, the LIG serves as both the ative electrodes and current collectors. For beter elee- trical connection, silver paint was applied on the common areas of the postive and negative electrode. The electrodes ‘were extended with conductive copper tapes and then connected to electrochemical workstation. To protect the contact pads from the electrolyte, Kapton polyimide tape was ceiployed 1 define the interdgitated area (FIG. 16C). Example 1.9, Characterization a SEM. images were taken on « FEI Quanta 400 high ‘resolution field emission insteument. The TEM and HRTEM ‘were performed using a 2100F fill emission gun, Aberr- tion-coreced scanning transmission elton microscopy (CsSIEM) images wore taken using an 80 KeV JEOL, ‘ARM200€ equipped with a spherical aberation coretoe ‘The LIG films were pete off and sonicated in chloroform before being transfered onto a C-lat TEM grid. X-ray pholoeletton spectroscopy (XPS) was performed using a PHT Quantera SXM Scanning X-ray Metoprobe with base pressure of Sxl0- Tore All of the survey spectra were recorded in 0.5 eV stp size with pss eney of 140 eV lemeatlspecia were recorded in 0.1 eV’ step sizes with pass energy of 26 eV All the spectra were corected using speaks (284.5 eV) as erences. X-ray diffraction (XRD) svas conducted on a Rigaku D/Max ultima II with Cu Ke radiation (1.54 A).A Renshaw Raman mieroscope sing Sld-am laser excitation at room temperature with laser power of § mW was employed to obtain Raman spectra. A Nicolet iniered speewoscope was used to acquire the FTIR. spectra, The surfice area of LIG was measured with a Quantachrome autosorbab BET surfce analyzer TGA (Q50, TA Instuments) themograms were carried out ‘peicen 100° C10 900°C. at $° C-min-! under argon; the ‘water content was caleulated fom the weight loss between room temperature and 100° C. The sheet resistances were measured using a Keitley four-point probe miter (mod: 195A, deteton limit: 20 MQ). The LIG samples for XRD, BET and TGA experiments were powder seratched f LG films. Other charatrizations were conducted directly ‘on LG fins. ” a4 ‘The crystallin size (.) along the c-axis and domain size in the a-axis (L,) and of LIG ave calulted from the etaracterstes ofthe XRD (002) and (100) peas using the gs 2 and 3, respectively > Lan rd > In the above equations, is the wavelength of the X-ray (Q=1.54 A) and By, (20) (in radian units) is the ful width at half-maximum of the peaks (200) and (100). Using Raman spectroscopic data, and calculating the crystalline size inthe a-axis (L,) from the ratio of integrated intensity of the G peak (Ig) and D peak (Ip), the F, can be obtained by eg 4 te ae tacenomat( 4) =e Inthe above equation, 2 is wavelength ofthe Raman laser Qy-$14 nm), Example 1.10, Measurements CY, galvanostatie CC measurements, and electrochemical inpedance spectoscopy (EIS) were peromed using a CHL 08D workstation (USA), All of measurements were conducted in ambient cotton for aqueous electrolytes (1 M HS0,). The LIG-MSCs using 1-uty!-3-methyimidazo- Jum tetrafliroborate (BMIM-BF,, Sigma-Aleich) were assembled and measured in an arpn-filed glovebox (VAC, model: NEXUS) with contlled O, and 1,0 levels lower than I ppm. To ensure fl difesion of fons onto surfaces of IG electrodes, the microdovies were soaked in electrolyte for 210 3 hbefore measurements. EIS was performed sing the simisoidal signal of 10 mV amplitude at frequency ranging from 10-mElz to 100 KHZ. Example 1.11. Caleuation of Parameters as Indications for Bleetrochemical Performance of LIG-MSCs ‘The specific areal capacitances (C,, in mP15 A in the on-petiodic direction. To obtain the density of states (DOS), Applicants used the teahedron method with Blichl corrections with a 45x71 kcpoints mesh, Example 2, Fabrication of Flexible Boron-Doped Laser Induced Graphene Microsupercapacitors In this Example, Applicants demonstrate that boron- oped porous graphene canbe prepared in ambient ar using 2 facile laser induction process from borc acid containing polyimide sheets. At the sme time, active electrodes can be pated for flexible micwsupercapacitors. Asa result of boron doping, the highest areal capacitance of s-prepared devices reaches 16.5 mem, three times higher than one x0 ” 4s 0 © 36 doped devices, with concomitant energy density inereases of 5 t 10 times at various power densities. The supeeb evela- bility and mechanical flexibility of the device is also well- ‘maintained. In particular, Applicants report in this Example that boron-doped L1G (B-LIG) can be synthesized with a laser induction method that is performed in air using a standard commercial laser writing tool as found in common machine shops. The synthesis starts by dissolving H,BO, into poly (pyromellitic dianhydride-co-44'-oxydlaniline amic acid) (or poly(amic acid), PAA) solution as a boron precursor, followed by condensation of the PAA to produce boric acid containing PI sheet. Subsequent laser induction using a ‘commercial CO, laser writes pattems on the as-prepared PI sheet under ambient conditions. During the laser induction, the surface ofthe PI sheet, with its H,BO,, transforms into B-LIG. At the same time, the B-LIG on the PI film can be patterned into interdigitated shapes for flexible MSCs. ‘The resulting B-LIG has significantly improved electrochemical performance over the non-dopes structures, with, three times higher capacitance and St 10 times higher energy density than Applicants achieved in pristine boron fre samples (eg. Example 1). The tansformation of PAA ‘© Pl is prefered lor the successful formation of LIG with, high electrochemical properties. Meanwhile the eyclability and Nexbility of as-prepared devices are well-maintained, demonstrating the poteatial of B-LIG materials for future low-cost energy storage devices FIG. 26A shows a scheme for the synthesis and patterning process of BLLIG materials for MSCs. Starting with a 12.8 Wi % PAA solution in NMP, various weight percentages of HBO, (0,1, 2,5 and 8 wt % relative to PAA) were added ‘and mixed under bath-sonicaton for 30 minutes to form a uniform precursor solution, Next, the solution was poured into an aluminum dish and the solvent removed i a vacuum coven at 60° C. for 3 days, resulting ina solid PAA/H,BO, sheet. The PAAVH,BO, sheet was then placed ina hydraulic press (Carver press) and heated to 200” C. for 30 min under a pressure of ~0.3 MPa to dehy date the PAA/H,BO, sheet ‘and form the PI'H,BO, film. During this step. PAA and 1,BO, will dehydrate and transform into PL and BO, as showa ia FIG. 268. The dehydeation trom PAA to PL is preferred for successful formation of LIG and will be Aiscussed in detail herein Finally, a standard CO, laser cutting system was used under ambient conditions to convert PVH,BO, to xB-LIG (0, 1,2, §,and 8, which denotes the initial HBO, loading weight percentages), Optical images of the PAA/H,BO, solution and patterned B-LIG on a PVH,BO, sheet are presented in FIG. 27 Here, the incorporation of HsBO, into the PAA was preferable, Attempts to incorporate boron from sources other than H,BO,, including ammonia borane and m-carborane, resulted in little or no boron doping of the L1G, Without being bound by theory, Applicants envision that this is because boric aid dehydrates and polymerizes on heating wile the other two evaporate or sublime, causing the fare ‘of boron doping. The major advantage of this synthetic process is that B-LIG can be fabricated and patterned atthe Same time during laser indvction, making it an ideal material for future rol-o-rll processing ‘The morphology of formed B-LIG was characterized using scanning electron microscopy (SEM) and transmission electron mieroscopy (TEM). FIG. 26C shows an SEM. image of the as-prepared SB-LIG that exhibits a porous structure due to the rapid formation of gascous products ding laser induetion, The inset in FIG. 26C reveals tat theUS 10,505,193 B2 37 thickness of SB-LIG on the Pl shet surface is -25 um. FIG. 26D shows the TEM image of SB-LIG at low magnification containing few-layer graphene structures with nanoscale ridges and wrinkles, which would be beneficial for higher accessible surface area and therefore enhanced eleciro- ‘chemical perfomance. High-resolution TEM (HRTEM) image in FIG, 268 fur ther confirms the graphitic nature ofthe SB-LIG nanosheet ‘Numerous graphene edges were found onthe surface ofthe SB-LIG nanosheet, again indicating @ highly accesible surface area, For comparison, L1G materials with different Foadingsof1,BO, (OB-L1G, IB-LIG, 2B-LIG, and 8B-LIG) were also prepared and imaged with SEM and TEM (FIGS, 28.29), No significant difference was found among. these Samples, indicating thot the loading of HBO, has litle «fect on the morphology of the resulting LIG, Raman spectroscopy and powder X-ray diffraction were further used to characterize the morphology of the B-LIG material. The Raman spectcum of SELIG in FIG. 304, shows three characteristic peaks for grapene derived mate rial: the D pk at ~1350 cm" induced by defects or disordered beat sites, the G peak at ~1590 em“ showing ophitc sp? carbon, and the 2D peak at ~2700 em” ‘originating from second order 2one boundary phonons. The large D peak observed here could arse from numerous sraphene edges, consistent with TEM observations (FIG. 268), boron doping into the L1G sheets, or the bending of the ‘raphene layers in the porous structure “The XRD pattem in F1G. 30B shows a prominent peak at 20-260, indicating an interiayer spacing of 3.4 A betw (002 arapitc crystal planes ia SBHLIG. A (100) graphitic crystal pase was also found at ‘The high degree of ‘rephitization of SB-LIG is also verified by thermogravie ‘metric analysis (IGA) measurement under argon (FIG. '30C). The PVH,BO, substrate begins to decompose at $80° (C, whereas SB-LIG remains stable over 900°C. From BET analysis (FIG, 31), the surface area of SB-LIG is 191 m*/a. FIG. 30D shows the pore size distibution of 3B-LIG, which swell <10 am 6 A 41 A sd.) “To confirm the boron doping inthe product, X-ray pho- toelecton spectroscopy (XPS) was performed on @ HyBOs- Joaded sample before and after laser indvtion as shown in FIG. 32 forsurvey speci and 1G. 33 for elemental spectra. Prior to laser inetion, the CIs peak originating from PVH,BO, could be fitted by thee sub-peaks: 2845, 285.6 and 288.4 eV, representing C—C, CN and C—-O—C—0 bonding, respectively (FIG. 334), For the Ols peak, two sub-peaks canbe found at 533.0 and $31.8 eV, representing ‘C—O and C=0 bonding (FIG. 338). After lose induction, the SB-LIG only showed a single prominent peak at 284.5 €¥ forCls and 532.9 eV for 01s, and the atomie percentage ‘of carbon increased from 72% to 84%, whereas oxygen creased from 19% to 4.3%, indicating that the imide group containing C—O bonding forms a graphite structure, Also, the Bis peak (FIG. 33C) shifted from 192.5 eV in B-PI down i 191.9 eV in $B-L1G after Ise induction, showing that boron in the LIG sheet was in the oxidized form (BCO,). The position of Nis changed litle afer laser treatment (FIG, 33D), but its atomic percentage dronped from 7.6% to 2.0%, again inicating that te imide group is the main reacting ste during laser induction proces. ‘To investigate the electrochemical properties of the BGLIG, it-was directly pattemed into interdigitated electrodes during laser induction and then fabricated into in- plane MSCs, as shown in FIG. MA. A solidstate electrolyte made from poly(vinyl sleohol) (PVA) and HS0, was used to ensure the flexibility of the deviee (as discussed in 5 x0 ” 4s 0 © 38 Example 3, Applicants have shown that polymeric eleetro- Iytes promote a batter electrochemical performance from IG than conventional aqueous eleclses). “To demonsrate the importance of the dehydration reac tion of PAA to Pl, PAA shoots wth o without H,BO, were direily laser induced and fabricated into MSC 10 fist compare ther electrochemical performance, Cyclic vltam- metry (CV) and eharge-dscharge (CC) measurements of coresponding MSC devices ate exhibited and compared in FIGS. 3MB-C. Both PAAslerived LIG-MSC and boron- doped PAAderived LIG-MSC showed smaller and tilted CV curves compared to horon-fieePl-lrived LIG-MSC in FIG. 348, repecsating a lower capacitance and a higher resistance: The lage vollage drop observe atthe iil Stage of discharge in in PA Acdesved LIGeMSC from FIG. SMC also inicates a higher intemal resistance, This rest shows thi the dehydration tp from PAA to PI is preferred for successful formation of B-LIG wih higher quality and better electrical conductivity ‘Next, Applicants compared the electrochemical perfor rance of BLIG with different inital HBO, loadings. Ata sean rate of O.l Vis, all CV curves ffom xB-LIG-MSCs (60, 1,2, 5, and 8) are pscudo-rectangula, as shown in FIG. 34D, representing good electrochemical double layer (EDL) character. Among them, SB-LIG-MSC shows the Jargst areal capacitance (C,), a8 evidenced by is highest CV cureat, From FIG. Mi; all galvanostate CC curves from B-LIG-MSCs at a current density of | mAfem? show 4 nearly twiangular shape, furher confirming the good capacitive behavior of the devices. Again, SB-LIG-MSC cits the longest discharge runtime, indicating the best capacitance pertormance, FIG. 34F shows the influence of boron coteat on C, which inreases from Oto SY reaching 4 maximum ~4 times greater than undoped:-LIG, and thea decreasing slghly at higher loadings. When the bora doping level is low, increasing boron dopants into L1G will increase the hole charge density ths enhancing the eeerons charg storage. However, afer a saturation threshold, adi- tional boron doping might induce more scaring sites for electrons in the L1G shoo, lowering the conductivity of the material, causing the decrease of C,. In ation, higher H,BO, loadings could inhibit the dehydration peocess of PAA, restiting in he retardation of ficient I formation. As ares, an optimum content of HBO, is needed 19 mxi- rie the device performance. case SBLIG-MSC shows the highest C, among dif ferent H,B0, loading samples, it was chosen to futher examine the electrochemical performance ofthe SB-LIG- MSC. FIG. 384 show CV curves ofa SBALIG-MSC at scan rates of O01, 0.02, 005 and 0410 Vis. The maintined pseudo-retangular shape of CV curves over diferent sean rates reresens goed EDL formation of the devices. IG. 388 shows the galvanostatie CC curves at diferent cureat densities (0.1, 02 and 0.5 mem?) all of which are early triangular, artherconfieming their optimal eapacitive behaviors, Additonal CV curves athigher san ates and CC curves at higher current densities are shoven in FIG. 36 0 demonstrate that SB-LIG-MSC can operate over a wide range of scan ates and eurent densities. The C, determined from these CC curves shows litle derease over curent densities covering two orders of magnitude, with a mexi- mum of 16.5 mElem: ata euret density f 005 mA/em", ‘which is four times lager than that ofthe nondoped LIG made from the same process without HBO, incorporate. Furhermore, C, of SB-LIG-MSC reasins over 3 mPlem? even when optated at a high eucent density of 40 mAVem*, indicating optimal power perfomanceUS 10,505,193 B2 39 Flectrochemical impedance measurements shown in FG. 37 furter demonstrate tht both extral and intemal resis tances of SBLLIG-MSC are lower than that of LIG-MSC. ‘These results indicate fester ionic transport and beter elee- tuode-eleciolyte interface when the LIG material doped with boron. The eycabilty of SBLLIG-MSCs was also tested over 12000 CC cycles at a cure density of 1.0 Alem? with over 99% of the capacitance retained (FIG. 35D), proving high stability of performance from the BLIG-MSC. In addition high C,, the assembled MSC from SB-LIG also shows optimal dirability under mechanical sts. When the device was bent and fixed (FIG. 386) at fret bending radi (rom 7 10 17 mum), the calculated C, from dlischage runtime remained essentially constant, as shown in FIG. 35F. Furhemore, ater 8000 bending cycles at radius of 10 mm, the C, ofthe device was unchanged (FIG. 35G), and CV curves during differen bending cycles. Shown in FIG, 38H are identical to each other, suggesting ‘at bending had litle effect onthe electrochemical perfor ‘mance of SB-LIG-MSC ‘To further demonstrate the high capability of SB-LIG- MSC over nonoped devives, a Ragose plot of volunetic power density (,) vs. snengy density () was compared fand shown ia FIG. 351. Under different P,. the Ey- of 2 SB-LIG-MSC was § to 10 times lager than that of L1G: MSC without boron doping. To better evaluate its commer cial potential, « Ragone plot of SB-LIG-MSC with specific areal energy density and power density is also provided in FIG. 38, The remarkable electrochemical performance, ‘yclabilty over chanre-ischarge times, and stability under bending makes B-LIG a promising candidate as an energy storage unit for nex-generation flexible and portable elec~ woaies. Insummary, Applicant report inthis Example a fueile and ‘robust laser induction process to prepare boroa-doped era phene structures from polyimide films, which can be used as ‘an. active material for Hlexible in-plane microsupercapacitors, With boron doping, the electrochemical peformance af B-LIG is enhanced with three times lager areal capacitance and $ to 10 times larger Volumetie energy density at various power densities. Als, the transformation of PAA to Pl is preferred for the suecessil formation of LIG with high quality and good electrochemical property. Meanwhile, the ‘eyclability and flexibility of the as-prepared device is well- ‘maintained, Considering the simplicity of material synthesis in ambient air and the easy device fabrication, horon-9 ‘mem: ata curent density of 0.02 m./em* over twice that ‘of conventional aqueous electrolytes. Moreover, laser induction on both sides of polyimide sheets enables the fabrication of vertically stacked supercapacitors to multiply its clectrochemical performance while preserving device lex- ibility. In particular, Applicants demonstrat in tis Example the fabrication of flexible laser induced graphene (LIG) based super capacitors (SCs) by using a soidstate polymeric electrolyte, poly(vinyl aleohol) (PVA) in H,S0,, TWo fex- ible, solid-state SCs are described: LIG-SCsand LIG-MSCs. ‘These devices show areal capacitance of >9 mFlem? at & discharge current density of 0.02 mA‘em*, which is over twice that achieved when using aqueous electrolytes, Fur thermore, by laser induction ofboth sides ofthe Pl sheets, solid state LIG-SCs can be stacked to form high density energy storage devices that multiply their eletrochemical performance while maintaining flexibility FIG. 398 schematically illustrates the process in fabri- cating fexbl, solid-state LIG-SCs, The process begins by first transforming the surface of a PI sheet into porous ‘raphene under laser induction using a commercially available, computer conrollsd CO. laser euting system, and then assembling either a single LIG-SC or stacked LIG-SC. FIGS. 4 and 398 show the photograph of halfside LIG electrode anda typical single LIG-SC device manually beat x0 ” 4s 0 © 42 to demonstrat its intrinsic lexiiliy: An advantage of this fabrication method sthat L1G ean be easily proce under ambient conditions on both sides of the PI shoct with 2 remaining ental insulating Pl layer separate them (FIG. 390), which then flitates layer-by-layer stacking of LIG- SCs Altematively, tis same technique ean also be used 0 patter LIG int intercigitated electrodes fr fabrication of solid state in-plane LIG-MSCs (FIG. 41). This one-step approach is both stghtforward and costelfectve, and could easily ft nto @ scalable, rollo-roll process for Jndstril production of graphene-hased energy slorage sjs- tems “The formed LIG showed very similar mogphology aad sraphene properties as the L1Gs in Examples 1-2. IG. 38C shows a cross sectional scanning eletcon microscope (SEM) image, where a thick LIG layer (-25 yn) is clay formed on both sides ofthe PI substrate after laser induction andi separated by an unexposed middle Pl layer that serves to electrically isolate the top and bottom LIG layers from cach other. The SEM image in FIG. 39D shows the porous structure of LIG and the transmission electron mieroscope CTEM) image ia FIG. 39E shows the nanoscale spples and ‘wrinkles inthe LIG films. Also, the high-tesofution TEM. (CARTEM) image in the inset of FIG. 39 reveals that these LG sheets contain numerous graphene edges resulting in more accesible surfice area and therefore better eleetro- chemical performance. “The Raman spectrum of LIG in FIG. 434 early shows three characteristic peaks of graphene derived material, specifically, a D peak at ~1380 em induced by defees, folding oe symumetry-broken carbon, G peak at ~15% em! generated by graphitic carbon and a2D peak at -2700em"" Criginating from second-order zone boundary phoaoes. ‘Without being bound by theory it is envisioned thatthe D peak could are from numerous graphene edges existing a LG fakes, which are also observed in the above TEM. images. “The XRD pattern in FIG. 438 shows prominent peak at 20-2560, indicative of an interlayer spacing of ~34 A between (002) graphitic crystal planes in L1G. The high degree of grophitization of LIG is futher supported by thermogravimewie analysis (TGA) under argon (FIG. 44), singe PI decomposes at ~$50° C., whereas LIG retains stable at >900° C. BET analysis in FIG. 45, shows thatthe suace area of LIG is ~330 meg witha pore size distb- tion betvoen 2-10 nm (FIG. 458), “To investigate its eletrochemical performance, LIG was fis fabricated into a flexible, single LIG-SC by sandwvich- ing a solid, polymeric eletrolyte (PVA and H,S0,) between two single-sided LIG-PI shoots which functioned both asthe ‘working electode and euret collector. The eyelcvoltam- metry (CV) curves shown in FIG, 424 were pseudo-roctan- ular over varying san ates (5, 10,20, and SO miVis), Which Js indicative of good EDL stability. In dition, FIG. 428, shows tht when dierent cuent densities (0.02, 0.08, 0.10, ‘und 0.20 mAlem*) were applied, the galvanostatie charge. discharge (CC) curves were neady triangular, indicating good capacitive behavior From the initial stge of dis- change, the negligible voltage drop shows that the device has Jow intemal resistance. Additonal CV carves at higher scan ates and CC curves at higher current densities ean be found in FIG. 46 1 show that LIG-SC can be charged and discharged over @ wide range of sean rates (5 to 1000 mV) and eurent densities (0.02 to 20 mAiem*). ‘The calculated areal capacitances (C.) from the CC curves with its comesponding eure detsites are shown in FIG. 42C, with the highest cxpaci-US 10,505,193 B2 B tance being 9.1] mem? at a conesponding curent density ‘of 001 mAlcm, comparable tothe values reported in the Titeratre for graphene based mierosuporcapacitors (Oto 2 imPlom?), Ao, the single LIG-SC shows excellent eyele stability, whore after 8000 CC cycles, the device retained over 98% ofits capacity (FIG. 42D), Next, the assembled single L.1G-SCs performance stabil ity was tested under mechanical bending. FIG. 47 com- pares the CV curves of a flexible single LIG-SC over Afferent bending di (12 mm to 24 mm) snd remarkably shows tat the bent device exhibits nearly identical behavior tothe fat LIG-SC. Also, FIG. 47B shows that the calculated CC, under diferent bending radi remind almost constant. From FIG. 47C, the C, was wellmaintsined after 7000 ‘bending eyeles aa radius of 14mm, indicating that epee ‘bending has ite effect on its electrochemical perfomance. “These findings further reinforce the assertion that LIG-SC is «promising candidat for energy storage devies in exible, portable and wearable electronics An additional advantage of the aforementioned method is the capability of forming L1G on both sides ofan iniviva PI sheet, thus enabling te fabrication of stacked LIG-SC (IG. 39), FIGS. 484-8 are illastations of a sores and parle LIG-SC assembled Irom stacked solidstate LIG- SC, where double-sided LG sheets are layered with ater- nating deposits of polymere eletolyte and eapped with single-sided LIG-PI shows. FIGS. 48C-D show the CC curves of a 3stack sods series and parallel LIG-SC, respectively. Compared to 2 single LIG-SC, the stacked series LIG-SC has a 2x higher working voltage window, ‘while the stacked parallel LIG-SC shows a 2« longer charge time when operated atthe same carent density, resuling ina 2x higher capacitance. In bot configurations, the CC curves present nesly’ triangular shapes with mins. cil voltage dap indicating negligible intemal and contact resistances. Additional CV and CC curves at various scan ates and current densities forthe tacked series and pallet LIG-SCs a shown in FIGS, 49.50 to demonstrate ther remarkable dduabilty over a wide range of scan rates and cureat densities, ven though the SCs ae stacked, the assembled stacked LIGASCS sill show high Bewibily. FIGS. 48E-F show thatthe capacitance ofthe tacked L.IG-SC circuits age nearly 100% of thei inital value, even afer being subjected to several thousand bending eyeles at a bending rads of 17 mm, Aditionaly, the CV curves at iferent bending cycles are nearly overlapped (insets of FIGS. 48E-F), indicating ‘well maintsinod flexibility “The laser induction process can also be wsed to synthesize ‘and patter LIG int intetiitate eletrodes fr the fabr- cation of inplane LIG-MSCs (FIG. 41). FIG. SLA is an ilustation of a Hexble LIG-MSC fabricated on a P shot that uses PYAHSO, os solid-state eletste. FIG. $18 shows CV curves ofthe LIG-MSC dove at diferent scan rates (0.01, 0.02, 005 and 0.1 Vis) with stable pseudo rectangular shape due 10 good EDL formation. FIG. S1C shows the galvanosatc CC curves of LIG=MSCs at different current densities (01, 0.2.03 and LO mAVem),allof which ‘ar nearly triangular due to their optimal capacitive behav~ iors. FIG. $2 shows addtional CV curves at higher scan rates and CC curves at higher cureat densities. The ealeu- lated C, from CC curves at diferent eurent densities are plated in FIG. S1D, where the devices strikingly exhibit a capacitance of greater than 9 mEiem’ ata curent density of ‘002 mAlem teresting, atthe sas euzeat densities the capacitances ofthe solid-state LIG-MSCS are tice that of ‘aqueous H,SO, eleeiolyte LIG-MSCs, Without being x0 ” 4s 0 © 44 bound by theory, itis envisioned that this improvement could come from the high hydrophobicity of the L1G mate- Fal and better interface formation between LIG electrodes and the organic polymer electoste, Fuahermore, capacitance of the soidstate LIG-MSCs remains over 19 mFlem®, even when operated ata higher current density of 30 mem’, indicating high power per formance of the device. Eletochemical impedance mea~ surements (FIG. 83) futher support faster ionic transport and. better eletrodeclectroly interlace in. LIG-MSCs Using PVAVHLSO, asthe elecirlyte. The near absen semicircle inthe ease of MSCs with PVA" imp there is high ionie conductivity’ atthe interface of the LIG cloctode ane polymer elecofye, Also the higher slope in the Nyquist plt for MSCs with PVAVH? indicates that they have more capacitive Behavior. The eyelbiity of solid-state LIG:-MSCs was also tested over 8000 CC eyces with <10% capacitance degradation (FIG. $4. In onder to test their circuit performance, two single LIG-MSC devies were connected in either eres or parallel configurations a shown {in FIG. 85. As expected, the working voage was doubled ‘when LIG-MSCs were in series, while the discharge runtime Jncreased nearly 100% whoa LIG-MSCs were in parle. a both cases, due tothe solid-state electrolyte the CC curves maintained their rianglar shape andthe LIG-MSC showed outstanding flexibility (FIG. SLA ins IG. SIE shows that the in-plane LIG-MSCs made from IG exhibits nearly 100% oF ts calculated capacitance less of bending ral. Similar wo he single LIGSC, CV curves of LIG-MSC over diffrent ending ead ae most identical to the ones inthe Hat devices (FIG. $6). After 7000 bending eyes, the capacitance remained at its intl value (FIG. S17), further supporting the universality oti laser induction method in producing energy storage units. Finally, FIG. 87 is 2 Ragone plot comparing single LIG-SCs and LIG-MSCs ia ether agucous or solid-state polymeric clecuoytes to commercially available eleoto- Ite capacitors and Li thin film batteries. Alhongh alumi- suum (AD electolytic capacitors deliver ultahigh power, their energy density is to onders of magnitude lower than LiG-derived devices. Simi, although fihium ion thin- fim bateries ean provide high energy density, thee power performance is tee orders of magitude lowe than ether Single LIG-SCs or LIG-MSCs. Interestingly, when com pared to LIG-MSC using 1M aqueous H,SO, as the tlecuolye,LIG-MSC witha solid-state polymer eecwolyte stores -2x more enn. Als, a comparison between single LIG-SCs and LIG-MSCs shows that LIG-MSCs have a higher power density than LIG-SC, likely duet the reduced jon diffasion length between the microcestodes in the LIGMSC device. Ragone plots of single LIG-SCs and LIG-MSCs with specie atal energy deasity and power density are also provided in FIG, 88 10 beter evaluate their commercial aplication potent In summary, Applicants have demonstrated hat by using a ese indoction process, commercially available polyimide substrates can be readily transformed into LIG and then fabricated into flexible and stackable SCs with enhanced capacitive performance. Iwo diferent devices, LIG-SCs and LIG-MSCs, wore fabricated using, PVAJH,SO, 26a solid polymeric eleowlyt and showed oustanding eletrochemical perfomance, cylbility, and fexbilty. The facile fab- ealion process fends itself well to commercial scalability Example 3.1. Materials Production and L1G ‘Supercapacitor Fabrication Kapton polyimide (PI, Cat. No. 2271K3, thickness 0.005") was purchased from MeMaster-Care and used 28

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