IP Library › Granted Patent US 12,331,410
Granted Patent B2
US 12,331,410 · App. 18/733,126 · Granted Jun 17, 2025

Graphene and the production of graphene

Inventors: René Hoffmann (Freiburg, DE); Christoph E. Nebel (Freiburg, DE); Sarah Roscher (Freiburg, DE)
Assignee: Avadain LLC
C25B1/00C01B32/19C01B32/198C25B9/19C25B9/40C25B11/043H01B1/04H01M4/587H01M4/625B82Y30/00B82Y40/00C01B2204/04C01P2002/82C01P2004/03C01P2004/24Y10S977/734Y10S977/842
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,331,410
App. No.
18/733,126
Granted
Jun 17, 2025
Kind
B2
Abstract

Compositions comprising hydrogenated and dehydrogenated graphite comprising a plurality of flakes. At least one flake in ten has a size in excess of ten square micrometers. For example, the flakes can have an average thickness of 10 atomic layers or less.

Claims (17)

1. An electrode comprising:

a reversibly hydrogenated graphite comprising a plurality of flakes having

at least one flake in 10 having a size in excess of 10 square micrometers,

a coefficient of determination value of 2D single peak fitting of μ-Raman spectra of the reversibly hydrogenated graphite after thermal treatment in inert atmosphere at 2 mbar and 800° C., collected at 532 nm excitation with a resolution better than 1.8 reciprocal centimeters, of larger than 0.99 for more than 50% of the spectra, and

a defect density characteristic of μ-Raman spectra of the hydrogenated graphite collected at 532 nm excitation with a resolution better than 1.8 reciprocal centimeters and an excitation power below 2 mW at the focus of an 100× objective having an average D/G area ratio being between 0.2 and 4, wherein at least 60% of the defects are reversible hydrogenation of sp 3 -hybridized carbon sites away from the edges of the flakes.

2. The electrode of claim 1 , wherein the majority of the defects are reversible hydrogenation of sp 3 -hybridized carbon sites away from the edges of the flakes.

3. The electrode of claim 1 , wherein more than 60% of μ-Raman spectra of the reversibly hydrogenated graphite have the coefficient of determination value larger than 0.99.

4. The electrode of claim 3 , wherein more than 40% of the μ-Raman spectra of the graphite have the coefficient of determination value larger than 0.995.

5. The electrode of claim 1 , wherein at least one flake in ten has a size in excess of 25 square micrometers.

6. The electrode of claim 1 , wherein the average thickness is seven atomic layers or less.

7. The electrode of claim 1 , wherein the defect density is characteristic of at least 50% of the μ-Raman spectra collected at 532 nm excitation with a resolution better than 1.8 reciprocal centimeters and an excitation power below 2 mW at the focus of an 100× objective having a D/G area ratio above 0.5.

8. The electrode of claim 1 , wherein the defect density is characteristic of at least 50% of the collected spectra having a D/G area ratio above 0.8.

9. The electrode of claim 1 , wherein the defect density is characteristic of the average D/G area ratio being between 0.4 and 2.

10. The electrode of claim 1 , wherein at least 5% of sp 3 hybridized carbon sites of the reversibly hydrogenated graphite are one or more of:

a) functionalized with a non-hydrogen chemical group,

b) cross-linked with sp 3 hybridized carbon sites of another flakes, or

c) otherwise chemically modified.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 4, 2024
From: HOFFMANN, RENÉ; NEBEL, CHRISTOPH E.; ROSCHER, SARAH
To: AVADAIN LLC
Reel/Frame 067614/0955 →
Priority Claims (1)
DE 102016202202.4 · Feb 12, 2016 · national
Continuity (5)
Division 17858906 · Jul 6, 2022
Continuation 16882579 · May 25, 2020
Continuation 15642086 · Jul 5, 2017
Continuation PCTEP2016073451 · Sep 30, 2016
Related Publication 20240327994A1 · Oct 3, 2024
References Cited (118)
US 4350576A · Watanabe et al. · 1982 [cited by applicant]
US 5503717A · Kang et al. · 1996 [cited by applicant]
US 9506156B2 · Dryfe et al. · 2016 [cited by applicant]
US 10662537B2 · Hoffmann et al. · 2020 [cited by applicant]
US 11066303B2 · Achee et al. · 2021 [cited by applicant]
US 20020008031A1 · Barsukov et al. · 2002 [cited by applicant]
US 20020168314A1 · Roemmler · 2002 [cited by applicant]
US 20060180477A1 · Avdeev et al. · 2006 [cited by applicant]
US 20070095674A1 · Reufer et al. · 2007 [cited by applicant]
US 20090155561A1 · Choi et al. · 2009 [cited by applicant]
US 20090308760A1 · Wei et al. · 2009 [cited by applicant]
US 20110059599A1 · Ward et al. · 2011 [cited by applicant]
US 20130156678A1 · Banerjee et al. · 2013 [cited by applicant]
US 20130302693A1 · Sun et al. · 2013 [cited by applicant]
US 20140017440A1 · Miyamoto · 2014 [cited by applicant]
US 20140080295A1 · Baldwin et al. · 2014 [cited by applicant]
US 20140131761A1 · Kwon et al. · 2014 [cited by applicant]
US 20140147648A1 · Zhamu et al. · 2014 [cited by applicant]
US 20140202744A1 · Kobayashi · 2014 [cited by examiner]
US 20140209480A1 · Cheng et al. · 2014 [cited by applicant]
US 20150021196A1 · Zahmu et al. · 2015 [cited by applicant]
US 20150027900A1 · Dryfe et al. · 2015 [cited by applicant]
US 20160124123A1 · Noro et al. · 2016 [cited by applicant]
US 20160298244A1 · Abdelkader et al. · 2016 [cited by applicant]
US 20160318766A1 · Georgiou · 2016 [cited by applicant]
US 20170081194A1 · Zhamu et al. · 2017 [cited by applicant]
US 20170298523A1 · Hoffmann et al. · 2017 [cited by applicant]
US 20180155520A1 · Nazarpour et al. · 2018 [cited by applicant]
US 20180190986A1 · Zhang et al. · 2018 [cited by applicant]
US 20180362349A1 · Zhong et al. · 2018 [cited by applicant]
US 20190233291A1 · Achee et al. · 2019 [cited by applicant]
US 20200223697A1 · Zhebelev · 2020 [cited by applicant]
US 20200283915A1 · Hoffmann et al. · 2020 [cited by applicant]
US 20210078863A1 · Roscher · 2021 [cited by applicant]
US 20220396486A1 · Roscher · 2022 [cited by applicant]
CN 102683389 · 2012 [cited by applicant]
CN 102807213 · 2012 [cited by applicant]
CN 103449402 · 2013 [cited by applicant]
CN 103693638 · 2014 [cited by applicant]
CN 104009237 · 2014 [cited by applicant]
CN 102923697 · 2014 [cited by applicant]
CN 104396077 · 2015 [cited by applicant]
CN 104709900 · 2015 [cited by applicant]
CN 106865534 · 2017 [cited by applicant]
CO 2017000713 · 2017 [cited by applicant]
EP 2878709 · 2015 [cited by applicant]
EP 2878709A1 · 2015 [cited by applicant]
EP 2982646 · 2016 [cited by applicant]
FR 2940965 · 2010 [cited by applicant]
GB 2523154 · 2015 [cited by applicant]
JP H11269685 · 1999 [cited by applicant]
JP 2008503059 · 2008 [cited by applicant]
JP 2009143799 · 2009 [cited by applicant]
JP 2013209261 · 2013 [cited by applicant]
JP 2014513659 · 2014 [cited by applicant]
JP 2015526382 · 2015 [cited by applicant]
JP 2016018695 · 2016 [cited by applicant]
KR 101494868 · 2015 [cited by applicant]
RU 2352029 · 2009 [cited by applicant]
RU 2625910 · 2017 [cited by applicant]
RU 2632688 · 2017 [cited by applicant]
WO WO2011136186 · 2011 [cited by applicant]
WO WO2012120264 · 2012 [cited by applicant]
WO WO2014191765 · 2014 [cited by applicant]
WO WO2015019093 · 2015 [cited by applicant]
WO WO2015131933 · 2015 [cited by applicant]
WO WO2016203388 · 2016 [cited by applicant]
WO WO2017137103 · 2017 [cited by applicant]
WO WO2018031591 · 2018 [cited by applicant]
Malard “Raman spectroscopy in graphene” Phys. Reports 473,51-87. (Year: 2009). [cited by examiner]
Abdelkader et al., “Continuous Electrochemical Exfoliation of Micrometer-Sized Graphene Using Synergistic Ion Intercalations and Organic Solvents,” ACS Pub., 2014, 6:1632-9. [cited by applicant]
Abdelkader et al., “Electrochemical exfoliation of graphite in quaternary ammonium-based deep eutectic solvents: A route for the mass production of graphane,” Nanoscale, 2015, 7(26)11386-92. [cited by applicant]
Achee et al., “High-yield scalable graphene nanosheet production from compressed graphite using electrochemical exfoliation,” Scientific Rep., Sep. 2018, 8:14525. [cited by applicant]
Bang et al., “Preparation of graphene with few defects using expanded graphite and rose bengal,” J. Mater. Chem., 2012, 22:4806-10. [cited by applicant]
Cancado et al., “Quantifying defects in graphene via Raman spectroscopy at different excitation energies,” Nano Lett., 2011, 11:3190-6. [cited by applicant]
Eigler et al., “Wet chemical synthesis of graphene,” Adv. Mater., 2013, 25:3583-7. [cited by applicant]
Elias et al., “Control of graphene's properties by reversible hydrogenation: evidence for graphene,” Science, 2009, 323:610-3. [cited by applicant]
Extended European Search Report in European Appln No. 22156746.4, dated May 9, 2022, 9 pages. [cited by applicant]
Felten “Single- and Double-Sided Chemical Functionalization of Bilayer Graphene,” Small, Feb. 2013, 9(4):631-639. [cited by applicant]
Ferrari et al., “Raman Spectrum of Graphene and Graphene Layers,” Phys. Rev. Lett., 2006, 97:187401. [cited by applicant]
Georgakilas et al., “Functionalization of Graphene: Covalent and Non-Covalent Approaches, Derivatives and Applications,” Chem. Rev., Sep. 2012, 112(11):6156-214. [cited by applicant]
Ghosh et al., “Dimensional crossover of thermal transport in few-layer graphene,” Nat. Mater., 2010, 9:555-8. [cited by applicant]
Hao et al., “The role of surface oxygen in the growth of large single-crystal graphene on copper,” Science, 2013, 342:720-3. [cited by applicant]
Hernandez et al., “High-yield production of graphene by liquid-phase exfoliation of graphite,” Nat. Nanotech., Sep. 2008, 3:563-8. [cited by applicant]
Hummers, Jr. and Offeman, “Preparation of Graphitic Oxide,” J. Am. Chem. Soc., Mar. 1958, 80:1339. [cited by applicant]
International Preliminary Report on Patentability in International Application No. PCT/EP2016/073451, mailed on Aug. 23, 2018, 9 pages. [cited by applicant]
International Preliminary Report on Patentability in International Appln. No. PCT/EP2020/075017, dated Mar. 24, 2022, 9 pages. [cited by applicant]
International Search Report and Written Opinion in International Application No. PCT/EP2016/073451, mailed on Nov. 16, 2016, 14 pages. [cited by applicant]
International Search Report and Written Opinion in International Appln. No. PCT/EP2020/075017, dated Nov. 20, 2020 , 15 pages. [cited by applicant]
Kang et al., “Effect of preparation conditions on the characteristics of exfoliated graphite,” Carbon, Aug. 2002, 40(9):1575-1581. [cited by applicant]
Khan et al., “Size selection of dispersed, exfoliated graphene flakes by controlled Centrifugation,” Carbon, 2012, 50(2):470-5. [cited by applicant]
Kumar et al., “Ultrahigh electrically and thermally conductive self-aligned graphene polymer composites using large-area reduced graphene oxides,” Carbon, 2016, 101:120-8. [cited by applicant]
Lee et al., “Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium,” Science, 2014, 344:286-9. [cited by applicant]
Paton et al., “Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids,” Nat. Mat., Jun. 2014, 13:624-30. [cited by applicant]
Pimenta et al., “Studying disorder in graphite-based systems by Raman spectroscopy,” Phys. Chem. Chem. Phys., 2007, 9:1276-90. [cited by applicant]
Pollard and Roy, “Graphene characterisation and standardisation via Raman spectroscopy,” Spectrosc. Eur., 2015, 27:9-12. [cited by applicant]
Randviir et al, “The oxygen reduction reaction at graphene modified electrodes,” Electroanalysis, Dec. 5, 2013, 26(1 ):76-83. [cited by applicant]
Roscher et al., “Abstract for High-yield electrochemical exfoliation of graphene using high potentials,” Poster presented at Graphene Conference, Dresden Germany, Jun. 26-29, 2018. [cited by applicant]
Roscher et al., “High voltage electrochemical exfoliation of graphite for high-yield graphene production,” RSC Adv., 2019, 9:29305-11. [cited by applicant]
Roscher et al., “High-yield electrochemical exfoliation of graphene using high potentials,” Poster presented at Graphene Conference, Dresden Germany, Jun. 26-29, 2018, (Abstract). [cited by applicant]
Sato et al., “D-band Raman intensity of graphitic materials as a function of laser energy and crystallite size,” Chemical Physics Letters, 2016, 427:117-121. [cited by applicant]
Schafer et al., “On the way to graphane-pronounced fluorescence of polyhydrogenated graphene,” Angew. Chem. Int. Ed., 2013, 52:754-7. [cited by applicant]
Shi et al., “Application of Pd/Graphene Modified Electrode in the Detection of 4-Chlorophenol,” Journal of Electrochemistry, Oct. 2015, 21(5): 488-495 (with English Abstract). [cited by applicant]
ube-ind.co.jp [online] “Excitation wavelength dependence of Raman spectrum of carbon material”, retrieved on Sep. 20, 2021, retrieved from URL < https://ube-ind.co.jp/usal/documents/s466_143.htm >, 1 page. [cited by applicant]
Uncertified Machine Translation of JP H11269685 (12 pages). [cited by applicant]
Wang et al., “High-Yield Synthesis of Few-Layer Graphene Flakes through Electrochemical Expansion of Graphite in Propylene Carbonate Electrolyte,” J. Amer. Chem. Society, Jun. 2011, 133(23):8888-91. [cited by applicant]
Wang et al., “Preparation of Graphene Sheets by Electrochemical Exfoliation of Graphite in Confined Space and Their Application in Transparent Conductive Films,” ACS Pub., 2017, 9:34456-66. [cited by applicant]
Wang et al., “Direct Growth of Graphene Film on Germanium Substrate,” Sci. Rep., 2013, 3:2465. [cited by applicant]
Whitener Jr. et al. “Graphene synthesis”, Diamond and Related Materials, Jun. 2014, 46:25-34. [cited by applicant]
Yang et al., “Development of Graphite and Its Derivatives,” Material Sciences, Aug. 2011, 25(8):53-57 (with Machine translation). [cited by applicant]
Yang et al., “Birch reduction of graphite. Edge and interior functionalization by hydrogen,” J. Am. Chem. Soc., Nov. 2012, 134:18689-94. [cited by applicant]
Yi et al., “Controllable functionalization and wettability transition of graphene-based films by an atomic oxygen strategy,” J Nanopart Res, Jul. 2, 2013, 15:1811, 14 pages. [cited by applicant]
Zhao et al., “Electrochemical generation of hydrogenated graphene flakes,” Carbon, Nov. 2014, 83:128-35. [cited by applicant]
Github.com [online], “Graphene Standards/ Raman: Graphene Raman evaluation,” Dec. 3, 2016, retrieved on Aug. 16, 2024, retrieved from URL<https://github.com/graphenestandards/raman>, 3 pages. [cited by applicant]
Github.com [online], “Graphene Standards/ Raman: Graphene Raman: 3-peak fitting of D, G and 2D,” Sep. 14, 2016, retrieved on Aug. 16, 2024, retrieved from URL<https://github.com/graphenestandards/raman>, 31 pages. [cited by applicant]
Imagej.net [online], “Introduction,” upon information and belief, no later than Jul. 5, 2017, retrieved on Aug. 16, 2024, retrieved from URL<https://imagej.net/ij/docs/intro.html>, 1 page. [cited by applicant]
Loudon's Organic Chemistry, 4th ed., Oxford University Press, 2002, Chapter 24, p. 1121. [cited by applicant]
Thomas-swan.co.uk [online], “Elicarb® Graphene Products,” Sep. 1, 2017, retrieved on Aug. 16, 2024, retrieved from URL<https://thomasswan.co.uk/wpcontent/uploads/2017/09/Elicarb-Graphene-Products-Advanced-Materials-LR.p… [cited by applicant]