WO2022066103A1 - Encres au graphène hautement conductrices pour impression 3d - Google Patents

Encres au graphène hautement conductrices pour impression 3d Download PDF

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Publication number
WO2022066103A1
WO2022066103A1 PCT/SG2021/050580 SG2021050580W WO2022066103A1 WO 2022066103 A1 WO2022066103 A1 WO 2022066103A1 SG 2021050580 W SG2021050580 W SG 2021050580W WO 2022066103 A1 WO2022066103 A1 WO 2022066103A1
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graphene
graphite
optionally
group
quaternary ammonium
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PCT/SG2021/050580
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English (en)
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Jiong LU
Jing Li
Feifei Wang
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National University Of Singapore
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Publication of WO2022066103A1 publication Critical patent/WO2022066103A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/135—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention provides an electrolyte composition that is useful in the exfoliation of graphite, a method of exfoliating graphite, a graphene product, conductive ink comprising the graphene, and supercapacitor comprising an electrode comprising the graphene.
  • graphene Due to its high conductivity, chemical stability and intrinsic flexibility, graphene is a prominent contender as a conductive medium for its application in energy storage devices, electronic displays and health diagnostics.
  • the electrolyte of the invention provides an improved exfoliation rate of graphite to provide graphene with high crystallinity and conductivity at high yields.
  • the electrolyte of the invention allows a reliable and rapid exfoliation of high conductive graphene at an economically competitive cost.
  • the graphene produced using the electrolyte may be useful in conductive inks for 3D printing, which allows the production of an electrode useful in supercapacitors.
  • An electrolyte composition for exfoliation of graphite comprising: a first quaternary ammonium salt; a second quaternary ammonium salt; and an electrolyte solvent, wherein: the first quaternary ammonium salt has the formula (R 1 ) 4 N + X- where each R 1 independently represents a linear C1.2 alkyl group and X- is a counterion; and the second quaternary ammonium species has the formula (R 2 )4N + Y; where each R 2 independently represents a linear or branched C5-24 hydrocarbyl group and Y _ is a counterion.
  • each R 2 group independently represents (e.g. one R 2 group represents) a linear or branched C5-18 alkyl group that is optionally interrupted by a phenylene group, which phenylene group is optionally substituted by one, two, or three C1.2 alkyl groups, optionally wherein each R 2 independently represents a linear or branched C5-8 alkyl group.
  • the molar ratio of the first quaternary ammonium salt to the second quaternary ammonium salt is from 1 :30 to 1:1, optionally from 1:20 to 1 :5, more optionally from 1:15 to 1:7, such as from 1 :13 to 1 :8, e.g. about 1:10.
  • electrolyte solvent comprises one or more of the group consisting of dimethylformamide, a glyme solvent, a cyclic carbonate, a linear carbonate, a cyclic ester, a linear ester, a cyclic or linear ether other than a glyme, a nitrile, dioxolane or a derivative thereof, ethylene sulfide, sulfolane, and sultone or a derivative thereof.
  • electrolyte composition according to any one of the preceding clauses, wherein the electrolyte solvent comprises a polar aprotic solvent, optionally wherein the polar aprotic solvent has a dielectric constant of from 30 to 100.
  • electrolyte solvent comprises one or more selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and N-Methyl-2- pyrrolidone, optionally wherein the electrolyte solvent comprises one or more selected from the group consisting of propylene carbonate and dimethylformamide.
  • a method of exfoliating graphite comprising the steps:
  • the potential difference is from about 0.5 to 20 V, optionally from about 0.5 to 10 V, such as about 1 to 7 V, for example about 1.5 to 6 V (e.g. about 2 to 5 V).
  • the method according to Clause 9 or 10 which method provides over 70% exfoliation of the graphite in the working electrode to graphene within 2 minutes from the application of the potential difference, optionally over 75%, such as over 80% (e.g. over 90%) exfoliation of the graphite in the working electrode to graphene within 2 minutes from the application of the potential difference, optionally wherein the method provides 70% exfoliation of the graphite in the working electrode to graphene within 20 seconds from the application of the potential difference.
  • the counter electrode comprises one or more selected from the group consisting of a metal and graphite, optionally wherein the counter electrode comprises one or more selected from the group consisting of stainless steel, titanium, nickel, platinum and graphite.
  • a graphene obtainable by the method according to any one of Clauses 8 to 14.
  • a graphene having a carrier mobility above 1000 cm 2 V' 1 s’ 1 , optionally having a carrier mobility above 1100 cm 2 V' 1 s’ 1 , such as above 1200 cm 2 V' 1 s’ 1 .
  • the graphene according to Clause 16 having an average area of from 2 to 2.5 pm 2 , such as about 2.3 pm 2 .
  • the conductive ink according to Clause 20 comprising from 1 to 10 wt. % graphene according to any one of Clauses 15 to 19, optionally from 3 to 7 wt. %, such as about 5 wt. %.
  • a supercapacitor comprising an electrode comprising a composite material formed from a graphene according to any one of Clauses 15 to 19 and MnC>2.
  • Figure 1 shows the electrochemical exfoliation of graphite foil with various substituted ammonium cations
  • Figure 2 shows the exfoliation of graphite in a propylene carbonate electrolyte with mixed ammonium cations, (a) l-V curve of graphite foil with different cathodic voltages applied, (b) The exfoliation yield of graphite foil as a function of tetrahexylammonium (THA) concentration in the electrolyte, (c-d) Photographs of graphite foil after a cathodic exfoliation at -5 V vs. Pt in propylene carbonate electrolyte containing 0.01 M tetramethylammonium (TMA) and 0.2 M tetrahexylammonium (THA).
  • TMA tetrahexylammonium
  • Figure 3 shows the structure characterization of exfoliated graphene, (a) Scanning transmission electron microscopic and (b) AFM images of as exfoliated graphene.
  • Inset in panel (a) shows the selected area electron diffraction pattern of graphene lattice, (c) The cross-sectional height profile and (d) Raman spectrum of graphene flakes as denoted in panel (b). The average lateral size and vertical thickness of as exfoliated graphene based on the AFM statistics, (g) FET device and (h) transport measurement of graphene flakes.
  • Figure 4 shows the C-C bond peak in the X-ray photoelectron spectroscopy spectrum for the exfoliated graphene.
  • Figure 5 shows the exfoliated graphene added into ink for 3D printing
  • (c) Photograph and (d) SEM image of printed 3D graphene framework (e) Galvanostatic charge-discharge curves, (f) rate performance, (j) cyclic voltammogram profiles and (h) electrochemical impedance spectroscopic plots of the MnO2- Graphene electrode in supercapacitor device.
  • the invention provides an electrolyte composition for exfoliation of graphite, comprising: a first quaternary ammonium salt; a second quaternary ammonium salt; and an electrolyte solvent, wherein: the first quaternary ammonium salt has the formula (R 1 )4N + X- where each R 1 independently represents a linear C1.2 alkyl group and X- is a counterion; and the second quaternary ammonium species has the formula (R 2 )4N + Y; where each R 2 independently represents a linear or branched C5-24 hydrocarbyl group and Y- is a counterion.
  • an “electrolyte composition” is a composition that may be used as an electrolyte in the electrochemical exfoliation of graphite to produce graphene.
  • the electrolyte composition of the invention comprises a liquid electrolyte solvent in which a first and second quaternary ammonium salt are dissolved.
  • the counterions X' and Y _ are not particularly limited and may be any counterion that is compatible with the electrolyte solvent and which is compatible for electrochemical exfoliation of graphite to produce graphene.
  • Suitable counterions include tetrafluoroborate (BF 4 -), hexafluorophosphate (PFe-), bromide (Br), chloride (Ck), hydrogen sulfate (HSO4'), hydroxide (OFT), nitrate (NOs-), perchlorate (CIO4-), phosphate (PO4 3- ), sulfate (SO4 2- )-
  • the first quaternary ammonium salt generally comprises a small cation, e.g. of the formula (R 1 ) 4 N + where each R 1 independently represents a linear C1.2 alkyl group. While the first quaternary ammonium salt comprises a small cation, this cation is highly solvated and so the overall solvated species is large. In contrast, the second quaternary ammonium salt comprises a large cation, e.g. of the formula (R 2 )4N + , where each R 2 independently represents a linear or branched C5-24 hydrocarbyl group and Y _ is a counterion.
  • the second quaternary ammonium salt is less highly solvated than the first quaternary ammonium salt, and so the overall solvated species is smaller than that of the first quaternary ammonium salt.
  • this difference in size of the solvates species is believed to result in different intercalation behaviour of the solvated species with the graphite that is to be exfoliated.
  • the smaller sized solvated species i.e. the larger cations, e.g. tetrahexylammonium
  • the larger solvated species i.e. the smaller cations, e.g. tetramethylammonium
  • synergistically peel off thin flakes from the graphite electrode i.e. the smaller cations, e.g. tetramethylammonium
  • the first quaternary ammonium salt comprises tetramethylammonium with a counterion.
  • the second quaternary ammonium salt has the formula (R 2 ) 4 N + Y; where each R 2 independently represents a linear or branched C5-24 hydrocarbyl group and Y- is a counterion.
  • each R 2 group independently a linear or branched C5- 18 alkyl group that is optionally interrupted by a phenylene group, which phenylene group is optionally substituted by one, two, or three C1.2 alkyl groups.
  • one or two e.g.
  • R 2 group may represent a linear or branched C5-18 alkyl group that is optionally interrupted by a phenylene group, which phenylene group is optionally substituted by one, two, or three C1.2 alkyl groups.
  • “interrupted” means that a C-C covalent bond in the alkyl chain is replaced by a phenylene group.
  • the phenylene group may be located at any position in the alkyl chain, and the connectivity of the alkyl chain on the phenylene group may be at any position (e.g. 1 ,2 [o/YPo]; 1 ,3 [meta]; or 1 ,4 [para]).
  • the linear or branched C5-18 alkyl group may be a linear or branched C5-14 alkyl group, such as a linear or branched C5-12 alkyl group, linear or branched C5-10 alkyl group, or linear or branched C5-8 alkyl group, all of which may be optionally interrupted by a phenylene group, which phenylene group is optionally substituted by one, two, or three C1.2 alkyl groups.
  • each R 2 independently represents a linear or branched C5-8 alkyl group.
  • the second quaternary ammonium salt comprises tetrahexylammonium with a counterion.
  • the second quaternary ammonium salt may be present in the electrolyte composition at a concentration of from 0.01 to 1 M, optionally from 0.05 to 0.5 M, more optionally from 0.1 to 0.8 M, such as from 0.15 to 0.6 M, for example about 0.2 M.
  • the molar ratio of the first quaternary ammonium salt to the second quaternary ammonium salt is from 1:30 to 1 :1 , optionally from 1 :20 to 1:5, more optionally from 1:15 to 1 :7, such as from 1 :13 to 1 :8, e.g. about 1 :10. Without being bound by theory it is believed that this ratio provides an optimised balance between the two intercalation behaviours of the different quaternary ammonium salts discussed above, leading to improved exfoliation rates and high graphene quality/yields.
  • Suitable solvents are well known to a person skilled in the art and include polar aprotic solvents, especially polar aprotic solvents having a dielectric constant of from about 30 to about 100.
  • Suitable solvents that may be used in some embodiments of the invention include one or more of the group consisting of a glyme solvent, a cyclic carbonate solvent, a linear carbonate solvent, a cyclic ester solvent, a linear ester solvent, a cyclic or linear ether solvent other than a glyme, a nitrile solvent, dioxolane or a derivative thereof, ethylene sulfide, sulfolane, and sultone or a derivative thereof.
  • a solvent that may be used in some embodiments of the invention is dimethylformamide.
  • Particular solvents that may be useful in embodiments of the invention disclosed herein include linear carbonate solvents and dimethylformamide.
  • the electrolyte solvent comprises one or more selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and N-Methyl-2-pyrrolidone.
  • Particular solvents that may be used in some embodiments of the invention include propylene carbonate and dimethylformamide.
  • the invention also provides a method of exfoliating graphite to produce graphene, using the electrolyte composition.
  • the invention provides a method of exfoliating graphite, comprising the steps:
  • the graphite working electrode is exfoliated by the electrolysis reaction and forms flakes of high quality graphene.
  • the potential difference may be from about 0.5 to 20 V.
  • a potential difference having a magnitude of below 0.5 V may be too low to result in exfoliation, while a potential difference with a magnitude of above 20 V may produce high amounts of heat and rapid decomposition the electrolyte, possibly leading to partial oxidation of the graphene.
  • the potential difference may be about 0.5 to 10 V, such as about 1 to 7 V, for example about 1.5 to 6 V (e.g. about 2 to 5 V).
  • the potential differences listed above refer to the magnitude of the potential difference.
  • the potential difference may be negative, i.e. a potential difference of -0.5 V to -20 V versus the counter electrode.
  • the counter electrode may also comprise graphite. In such embodiments, an alternating current may be used in order to generate graphene from both electrodes.
  • the method of the invention rapidly provides high yields of graphene.
  • the method provides over 70% exfoliation of the graphite in the working electrode to graphene within 2 minutes from the application of the potential difference.
  • the method may provide a 70% yield of graphene within 2 minutes from the application of the potential difference.
  • the method may provide over 75%, such as over 80% (e.g. over 90%) exfoliation of the graphite in the working electrode to graphene within 2 minutes from the application of the potential difference.
  • the method provides 70% exfoliation of the graphite in the working electrode to graphene within 20 seconds from the application of the potential difference.
  • the working electrode comprises graphite that is to be exfoliated.
  • the counter electrode may comprise any suitable material.
  • the counter electrode may comprise one or more selected from the group consisting of a metal and graphite.
  • the counter electrode may comprise one or more selected from the group consisting of stainless steel, titanium, nickel, platinum and graphite.
  • the graphite in the working/counter electrodes may be graphite foil.
  • the invention provides a graphene obtainable by the method of the invention.
  • the invention provides a graphene having a carrier mobility above 1000 cm 2 V' 1 s’ 1 , for example having a carrier mobility above 1100 cm 2 V' 1 s’ 1 , such as having a carrier mobility above 1200 cm 2 V' 1 s -1
  • the graphene of the invention may have an average area of from 2 to 2.5 pm 2 , such as about 2.3 pm 2 .
  • the graphene of the invention may have an average thickness of from 2 to 3 nm, such as about 2.6 nm.
  • the graphene of the invention may have less than 3 molar% oxygen.
  • the invention also provides a conductive ink for 3D printing, comprising a graphene according to the invention.
  • the conductive ink for 3D printing may comprise from 1 to 10 wt. % graphene according to the invention, optionally from 3 to 7 wt. %, such as about 5 wt. %.
  • the invention also provides a supercapacitor comprising an electrode comprising a composite material formed from a graphene according to the invention and MnC>2.
  • the invention is able to rapidly provide extremely high quality and high value graphene at high yields from very low cost graphite precursors, using simple reagents and apparatus. This is demonstrated further in the below Examples. Examples
  • the electrochemical exfoliation of graphite was conducted using an electrochemical workstation (CHI 760E) consisting of a two electrode system.
  • Graphite foil e.g. L.T Graphite, Shanghai, China
  • the electrolyte was a non-aqueous solution consisting of 0.2 M tetrahexyl ammonium and 0.02 M tetramethyl ammonium in propylene carbonate (PC).
  • PC propylene carbonate
  • the intercalated graphite can immediately expand and detach into solution, a constant voltage is applied until the thorough detachment of the graphite into electrolyte.
  • the intercalated graphite was collected via filtration, and further washed with water 3 times to eliminate the organic residuals. Finally the intercalated graphite can be further dispersed into desired solvents via bath sonication with a power of 100 W for 0.5 h to provide a uniform graphene dispersion.
  • Tetra-methyl ammonium cations offer fast intercalation and delamination of graphite foil, which can readily disintegrate graphite foil into powders in 2 minutes with a high yield (approaching 100%). Longer alkyl chains and branched hydrocarbyl groups generally showed slower intercalation kinetics, resulting in thicker flakes and lower yields of graphene. Scanning electron microscopy images in Figure 1c reveal that solvated TMA cations only enter the inter-space between graphite powders rather than graphite interlayers.
  • DMF is a cheaper solvent than PC, it may advantageously be used to provide high quality graphene at lower cost.
  • exfoliated graphene The structure and electrical properties of exfoliated graphene was characterized as shown in Figure 3. Scanning transmission electron microscopy shows that exfoliated graphene reveals an intact atomic lattice in large area. A statistical analysis of multiple atomic force microscopy (AFM) images reveals that exfoliated graphene exhibits an average size of 2.3 pm 2 with an average thickness of 2.6 nm. Electrical transport measurement indicates a record high carrier mobility around 1200 cm2 V-1 s-1 , surpassing the best result of solution- exfoliated graphene (405 cm 2 V' 1 S’ 1 , J. Am. Chem. Soc. 2015, 137, 13927-13932).
  • AFM atomic force microscopy
  • Exfoliated graphene may be formulated into a conductive ink for 3D printing.
  • the inventors have developed a cathodic exfoliation method using an electrolyte comprising mixed ammonium cations that is able to rapidly produce high quality graphene flakes.
  • the method provides an easily scalable route for the synthesis of highly conductive graphene flakes with a high yield (> 70%) and production rate (>1 Kg/h).
  • Atomically thin graphene flakes reveal record high carrier mobility and excellent solution processibility, which can be easily formulated into ink for 3D printing of functional architectures and devices with remarkable conductivity.

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Abstract

L'invention concerne une composition d'électrolyte destinée à exfolier du graphite, comprenant : un premier sel d'ammonium quaternaire ; un second sel d'ammonium quaternaire ; et un solvant d'électrolyte. La composition d'électrolyte peut être utilisée dans l'exfoliation de graphite, afin de fournir du graphène. Le graphène peut être utile dans l'impression 3D et la formation de supercondensateurs.
PCT/SG2021/050580 2020-09-24 2021-09-24 Encres au graphène hautement conductrices pour impression 3d WO2022066103A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140061059A1 (en) * 2011-03-10 2014-03-06 The University Of Manchester Production of graphene
CN109553093A (zh) * 2018-12-29 2019-04-02 厦门十维科技有限公司 电化学溶胀制备石墨烯分散液的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140061059A1 (en) * 2011-03-10 2014-03-06 The University Of Manchester Production of graphene
CN109553093A (zh) * 2018-12-29 2019-04-02 厦门十维科技有限公司 电化学溶胀制备石墨烯分散液的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LIU ZHAOYANG, ZHANG HENG, EREDIA MATILDE, QIU HAIXIN, BAAZIZ WALID, ERSEN OVIDIU, CIESIELSKI ARTUR, BONN MISCHA, WANG HAI I., SAMO: "Water-Dispersed High-Quality Graphene: A Green Solution for Efficient Energy Storage Applications", ACS NANO, AMERICAN CHEMICAL SOCIETY, US, vol. 13, no. 8, 27 August 2019 (2019-08-27), US , pages 9431 - 9441, XP055929038, ISSN: 1936-0851, DOI: 10.1021/acsnano.9b04232 *
YAO BIN, CHANDRASEKARAN SWETHA, ZHANG JING, XIAO WANG, QIAN FANG, ZHU CHENG, DUOSS ERIC B., SPADACCINI CHRISTOPHER M., WORSLEY MAR: "Efficient 3D Printed Pseudocapacitive Electrodes with Ultrahigh MnO2 Loading", JOULE, CELL PRESS, vol. 3, no. 2, 1 February 2019 (2019-02-01), pages 459 - 470, XP055929047, ISSN: 2542-4351, DOI: 10.1016/j.joule.2018.09.020 *
ZHANG YUAN, XU YOULONG: "Simultaneous Electrochemical Dual‐Electrode Exfoliation of Graphite toward Scalable Production of High‐Quality Graphene", ADVANCED FUNCTIONAL MATERIALS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 29, no. 37, 1 September 2019 (2019-09-01), DE , XP055929040, ISSN: 1616-301X, DOI: 10.1002/adfm.201902171 *

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