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Spray deposition of supercapacitor electrodes using environmentally friendly aqueous activated graphene and activated carbon dispersions for industrial implementation
Umeå University, Faculty of Science and Technology, Department of Physics.ORCID iD: 0000-0002-3881-6764
Umeå University, Faculty of Science and Technology, Department of Physics.
Umeå University, Faculty of Science and Technology, Department of Physics.ORCID iD: 0000-0002-8438-2581
Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA) Alava Technology Park, Vitoria-Gasteiz, Spain.
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2021 (English)In: ChemElectroChem, E-ISSN 2196-0216, Vol. 8, no 7, p. 1349-1361Article in journal (Refereed) Published
Abstract [en]

A spray gun machine was used to deposit high‐surface‐area supercapacitor electrodes using green non‐toxic aqueous dispersions based on different kinds of high specific surface area nanostructured carbon materials: activated graphene (a‐rGO) and activated carbon (AC). Tuning the spray conditions and dispersion formulation allowed us to achieve good adhesion to stainless‐steel current collectors in combination with high surface area and a satisfactory mechanical stability of the electrodes. The specific surface area of approximately 2000 m2/g was measured directly on a‐rGO and AC electrodes showing only around a 20 % decrease compared to the precursor powder materials. The performance of the electrodes deposited on stainless‐steel and aluminum current collectors was tested in supercapacitor devices using three electrolytes. The electrodes were tested in an “as‐deposited” state and after post‐deposition annealing at 200 °C. The spray deposition method and post‐deposition annealing are completely compatible with roll‐to‐roll industrial production methods. The a‐rGO demonstrated superior performance compared to AC in supercapacitor electrodes with gravimetric capacitance, energy, and power density parameters, which exceed commercially available analogues. The formulation of the dispersions used in this study is environmentally friendly, as it is based on only on water as a solvent and commercially available non‐toxic additives (graphene oxide, fumed silica, and carbon nanotubes).

Place, publisher, year, edition, pages
John Wiley & Sons, 2021. Vol. 8, no 7, p. 1349-1361
Keywords [en]
graphene, supercapacitors, spray deposition, electrodes, surface area
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-182241DOI: 10.1002/celc.202100235ISI: 000664256200015Scopus ID: 2-s2.0-85108297157OAI: oai:DiVA.org:umu-182241DiVA, id: diva2:1544111
Funder
Swedish Research Council, 2017‐04173EU, Horizon 2020, 881603Available from: 2021-04-14 Created: 2021-04-14 Last updated: 2023-09-05Bibliographically approved
In thesis
1. Properties and applications of materials based on graphite oxide
Open this publication in new window or tab >>Properties and applications of materials based on graphite oxide
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Egenskaper och tillämpningar av material baserade på grafitoxid
Abstract [en]

Graphite oxide (GO) is a hydrophilic, layered material prepared by oxidation of graphite. In the first part of this thesis, we studied materials produced from GO by intercalation and functionalization. The second part of the thesis was focused on supercapacitor applications of high surface area carbons prepared from GO using chemical activation. 

A detailed study of acetylated GO (AcGO) was performed to verify structure and properties of this material. Reports from 1960’s suggested that AcGO has “pillared” structure. Our analysis showed that the AcGO demonstrates expanded structure due to acetylation but exhibits negligible specific surface area and should not be considered as a pillared material. 

Pillared reduced GO (prGO) was prepared by applying mild annealing to GO material pillared with tetrapod-shaped amine molecules. PrGO showed relatively high surface area due to remaining pillaring molecules in the structure. The prGO is hydrophobic and exhibits 100x improved conductivity compared to precursor. PrGO is one of few true pillared structures reported in literature so far, and the first ever prepared starting from pillared GO.

We also investigated the sorption of common dyes, methylene blue (MB), rose bengal (RB) and crystal violet (CV), by multilayered graphene oxide materials. We found that MB dissolved in ethanol intercalates the GO structure, as evidenced by significant expansion of inter-layer distance, and increase in weight due to sorption. In contrast to MB, GO is not easily intercalated by CV and RB dyes. We believe that the flat MB molecule shape allows easier insertion between GO layers compared to twisted and non-flat CV and RB molecules. Our results suggest that penetration into GO inter-layers depends not only on the size of molecules, but also on the shape.

Temperature dependent study of structures formed by Brodie GO (BGO) in liquid alkyl alcohols was performed for a set starting from undecyl alcohol (no. of C=11) and up to behenyl alcohol (no. of C=22). We found that BGO exhibits strong swelling in all molten alcohols in this set. Heating just above the melting point of alcohol results in expansion of inter-layer distance of GO due to intercalation of two layers of alcohol molecules in orientation perpendicular to graphene oxide planes (α-phase). Further heating of α-phase results in incongruent melting and formation of new phase with significantly smaller inter-layer distance and amount of intercalated alcohol (β-phase). The transition from α-to β-phase is distinctly different compared to swelling transitions previously observed for BGO in smaller alcohols (no. of C<10). A more detailed study of the BGO-C16 system revealed that β-phase has structure with alcohol molecules forming layers mostly in parallel to graphene oxide orientation.

In the second part of this thesis we studied activated reduced GO (a-rGO) as electrode material in supercapacitors. A-rGO is a high surface material (~3000 m2g-1) obtained by KOH activation of rGO. We developed formulations for stable aqueous dispersions of a-rGO optimized for preparation of electrodes by semi-industrial spray-gun deposition. The electrodes prepared by spray deposition showed energy storage parameters only slightly lower compared to lab scale blade-deposited electrodes. Spray-gun deposition might provide significant advantage for industry over conventional methods to prepare electrodes from a-rGO. 

We also applied KOH activation procedure, optimized for producing high surface area a-rGO, to biochar prepared from pine cones. Using this cost free “waste” picked up in Umeå region forest we produced high quality activated carbon very similar to a-rGO in terms of structure, pore size and surface area. Overall, the energy storage parameters of electrodes prepared using the activated carbon from pine cones were on the same level as a-rGO electrodes, which are produced by a lot more complex and expensive chemical treatments.

Place, publisher, year, edition, pages
Umeå: Umeå Universitet, 2023. p. 86
Keywords
Graphene, Graphite Oxide, Graphene Oxide, Swelling, Phase Transition, Intercalation, Activated Graphene, Activated Carbon, Supercapacitors, Neutron Reflectometry
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:umu:diva-214116 (URN)978-91-8070-102-0 (ISBN)978-91-8070-103-7 (ISBN)
Public defence
2023-09-29, NAT.D.480, Naturvetarhuset, Umeå, 13:00 (English)
Opponent
Supervisors
Available from: 2023-09-08 Created: 2023-09-05 Last updated: 2023-09-05Bibliographically approved

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Boulanger, NicolasSkrypnychuk, VasylNordenström, AndreasTalyzin, Alexandr V.

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