Nanostructured Electromaterials for Energy Applications
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This document summarizes research on using nanostructured electromaterials for energy applications. It discusses using precision assembly of nano- and micro-dimensional components into macroscopic structures to improve device performance. Specific examples discussed include using porphyrins, conducting polymers, and graphene in dye-sensitized solar cells, hydrogen production, and nanostructure fabrication. The goal is to create the next generation of electrochemical devices through 3D assembly of electromaterials at the nano- and micro-scale.
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Nanostructured Electromaterials for Energy Applications
- 1. Nanostructured Electromaterials for Energy Applications David L. Officer Professor of Organic Chemistry Intelligent Polymer Research Institute University of Wollongong davido@uow.edu.au ACES – The European Dimension NCSR, DCU, Dublin 21 May 2015
- 2. To create the next generation of electrochemical devices via the precision assembly of nano-/micro- dimensional components into macroscopic structures to deliver unprecedented device performance. The Vision
- 3. The ACES II Structure 2014-2021
- 4. 3D Electromaterials Theme Structural materials Characterisation Electromaterials Modelling Fabrication Reaction centres
- 7. Dye Sensitized Solar Cell (DSSC) “Grätzel Cell” Photoelectrochemical Cell DSCC Efficiency: Lab >12% Production 8 - 10% Director of the Laboratory of Photonics and Interfaces, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland. B. O’Regan, M. Grätzel, Nature 1991, 353, 737−740 7
- 8. M. Grätzel, Inorganic Chemistry, 2005, 44, 6841 8 Operation of the DSSC
- 9. 9 Cherian, S.; Wamser, C. C. J. Phys. Chem. B, 2000, 104, 3624. TCPP = 3.0% Zn-2 = 4.8% Voc = 660 mV Isc = 9.70 mA cm-2 FF = 0.75 Electrolyte = 1376 Solvent = THF Md. K. Nazeeruddin, R. Humphry-Baker, D. L. Officer, W. M. Campbell, A. K. Burrell, M. Grätzel, Langmuir, 2004, 20, 6514-6517. GD2 = 6.1% Voc = 685 mV Isc = 13.3 mA cm-2 FF = 0.68 Electrolyte = 1376 Solvent = THF = 7.1% Voc = 660 mV Isc = 9.70 mA cm-2 FF = 0.75 Electrolyte = 1376 Solvent = THF Campbell, W. M.; Jolley, K. W.; Wagner, P.; Wagner, K.; Walsh, P. J.; Gordon, K.; Schmidt-Mende, L.; Nazeeruddin, M. K.; Wang, Q.; Graetzel, M.; Officer, D. L., J. Phys. Chem. C 2007, 111,11760. GD1 = 5.2% Voc = 566 mV Isc = 13.5 mA cm-2 FF = 0.68 Electrolyte = 1376 Solvent = THF Wang, Q.; Campbell, W. M.; Bonfantini, E. E.; Jolley, K. W.; Officer, D. L.; Walsh, P. J.; Gordon, K.; Humphry-Baker, R.; Nazeeruddin, M. K.; Graetzel, M., J. Phys. Chem. B 2005, 109, 15397. Porphyrin dye improvement
- 10. X-ray reflectometry analysis of porphyrins on TiO2 10 X-ray reflectometry results for porphyrins bound to dry amorphous ALD TiO2 coating on quartz. M.J. Griffith, M. James, G. Triani, P. Wagner, D.L. Officer, G.G. Wallace Langmuir 2011, 27,12944.
- 11. 11 M.J. Griffith, M. James, G. Triani, P. Wagner, D.L. Officer, G.G. Wallace Langmuir 2011, 27,12944. X-ray reflectometry analysis of porphyrins on TiO2
- 12. 12 Inactive porphyrin dye on TiO2 surface Coexistence of Femtosecond- and Non-electron-injecting Dyes in Dye- Sensitized Solar Cells: Inhomogeniety Limits the Efficiency Kenji Sunahara,†,‡ Akihiro Furube,*,†,‡ Ryuzi Katoh,‡ Shogo Mori,§ Matthew J. Griffith,|| Gordon G. Wallace,|| Pawel Wagner,|| David L. Officer, || and Attila J. Mozer || †Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan, ‡National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan, §Department of Fine Materials Engineering, Shinshu University, Nagano, 386-8567, Japan, and ||Intelligent Polymer Research Institute, ARC Centre for Excellence for Electromaterials Science, University of Wollongong, Wollongong 2522, Australia CORRESPONDING AUTHOR FOOTNOTE *E-maill: akihiro-furube@aist.go.jp J. Phys. Chem. C, 2011, 115 (44), pp 22084–22088 ABSTRACT We performed a detailed and quantitative spectroscopic study of the electron injection dynamics for porphyrin ....... By comparing the dynamics of two of the most studied porphyrins with those of a Ru-complex (N719), we have directly elucidated that the short-circuit current for the porphyrin sensitized solar cells is limited by the presence of excited dyes that are quenched in the sub-ns time range without competing with the electron injection process, even though both porphyrins shows faster injection processes within the ps time range than N719.
- 13. Hydrogen Using porphyrins to create an artificial reaction centre
- 14. 14 Mimicking the reaction centre in photosynthesis With Prof Les Dutton Johnson Research Foundation, Department of Biochemistry and Biophysics University of Pennsylvania. Philadelphia PA USA ARC Artificial Photosynthesis Discovery project 2012-2014
- 15. Pigment Protein Binding Dynamics NR174 Maquette-bound porphyrin Free porphyrin
- 16. Hydrogen 16 Making porphyrin/maquette dye sensitised solar cells /Maquette
- 17. Device MeasurementsPorphyrin based devices using 2.6 µm TiO2 : Porphyrin/maquette devices using 2.6 µm TiO2 : Maquette/Porphyrin 1 : 1.1 (At a concentration of 90.8 µM porphyrin) Voc (mV) Jsc (mA/cm2) Fill Factor Efficiency (%) Porphyrin Quantity (nano-mol.cm-2.µm-1) Sensitized Porphyrin 607.5 (± 16.6) 2.50 (± 0.16) 0.60 (± 0.03) 0.92 (± 0.05) 13.5(± 0.5) Porphyrin Salt 620 (± 16.4) 1.20 (± 0.12) 0.52 (± 0.04) 0.39 (± 0.07) 5.7 (± 1.2)* Maquette-Porphyrin Ensemble 720 (± 8.7) 1.66 (± 0.15) 0.78 (±0.01) 0.93 (± 0.09) 3.5 (± 0.1) DSSC Device Comparative Results- 2.5 µm transparent TiO2 using iodide/triiodide redox electrolyte in acetonitrile (n=4, ± StdDev)
- 18. Binds in seconds 17 Dimer porphyrins binding to maquettes Nick Roach Rhys Mitchell
- 19. 18 Dimer porphyrins binding to maquettes
- 20. Hydrogen Using porphyrins to create nanostructures
- 21. Using porphyrins to exfoliate graphene Jenny Malig, Adam W. I. Stephenson, Pawel Wagner, Gordon G. Wallace, David L. Officer and Dirk M. Guldi, Chem. Commun., 2012, 48, 8745–8747 M = H or Zn R = CN or CO2H Pawel Wagner
- 22. Kiessling, D.; Costa, R. D.; Katsukis, G.; Malig, J.; Lodermeyer, F.; Feihl, S.; Roth, A.; Wibmer, L.; Kehrer, M.; Volland, M.; Wagner, P.; Wallace, G. G.; Officer, D. L.; Guldi, D. M., Novel nanographene/porphyrin hybrids - preparation, characterization, and application in solar energy conversion schemes. Chemical Science 2013, 4 (8), 3085-3098. Using porphyrins to exfoliate graphene ....... and bind nanoparticles ……. and make solar cells
- 23. 23 Hydrogen Using graphenes to create nanostructures
- 25. Chemically converted graphene (CCG) Graphene oxide (GO) Graphene (CCG)
- 26. Natural flake graphite 12 The electrodes, which started out as calcined petro pitch are now fully graphitized articles. At this fin graphitized calcined petroleum coke particles held matrix, which may contain graphitized petroleum secondary impregnation. The form of the carbon in the heat treated electrod starting carbon. The electrode started out as an am crystalline order defined by the mesophase from w heat treated article is composed of carbon atoms a What began as relatively low end petroleum by-pr value versatile form of carbon that has literally hu The ac synthet Materi picture Natural lump graphite >99.9% graphite Synthetic graphite from petroleum coke Graphite is not just graphite 26
- 27. A Simple Route to Aqueous Graphene Dispersions R. Jalili, S. H. Aboutalebi, D. Esrafilzadeh, K. Konstantinov, J. M. Razal, S. E. Moulton and G. G. Wallace, Material Horizons 1, 87-91, (2014). Liquid crystalline graphene oxide (GO) Chemically converted graphene (CCG) D. Li, M. B. Müller, S. Gilje, R. B. Kaner and G. G. Wallace, Nature Nanotechnology 2008, 3, 101-108.
- 28. CCG aqueous and organic solvent dispersions rCCG in DMF (0.5 mg/ml)rCCG dispersion diluted with different solvents “Organic Dispersions of Highly Reduced Chemically Converted Graphene.” S. Gambhir, E. Murray, S. Sayyar, G. G. Wallace and D. L. Officer, Carbon 2014, online. . CCGaq CCG in water (0.5 mg/ml)
- 29. Costa, R. D.; Feihl, S.; Kahnt, A.; Gambhir, S.; Officer, D. L.; Wallace, G. G.; Lucio, M. I.; Herrero, M. A.; Vazquez, E.; Syrgiannis, Z.; Prato, M.; Guldi, D. M., Carbon Nanohorns as Integrative Materials for Efficient Dye- Sensitized Solar Cells. Advanced Materials (Weinheim, Germany) 2013, 25, (45), 6513-6518. Carbon nanomaterials for dye sensitised solar cells Different nanocarbons such as SWCNTs, graphene, SWCNHs, and their respective oxidized products have been used to fabricate novel nanocarbon/TiO2 photolectrodes for DSSCs Upper: J−V characteristics for DSSCs prepared with the different nanocarbon/TiO2 photoelectrodes – reference (black solid), 0.5 wt% SWCNH (black dashed), 0.2 wt% SWCNHox (black dotted), 0.1 wt% graphene (dark grey solid), 0.5 wt% grapheneox (dark grey dashed), 0.1 wt% SWCNT (dark grey dotted), and 0.1 wt% SWCNTox (light grey solid). Lower: Incident monochromatic photo-to-current conversion efficiency (IPCE) of the different nanocarbon/TiO2 photoelectrodes – reference (black solid), 0.5 wt% SWCNH (black dashed), 0.2 wt% SWCNHox (black dotted), 0.1 wt% graphene (dark grey solid), 0.5 wt% grapheneox (dark grey dashed), 0.1 wt% SWCNT (dark grey dotted), and 0.1 wt% SWCNTox (light grey solid). Ref. graphene
- 30. IPRI/ACES DLO 230813 Aqueous liquid crystalline graphene oxide (LC-GO) Organic Solvent-Based Graphene Oxide Liquid Crystals: A Facile Route toward the Next Generation of Self-Assembled Layer-by-Layer Multifunctional 3D Architectures Rouhollah Jalili, Seyed Hamed Aboutalebi, Dorna Esrafilzadeh, Konstantin Konstantinov, Simon E. Moulton, Joselito M. Razal and Gordon G. Wallace ACS Nano 2013, 7 (5), 3981–3990. • Self-assembly of ultralarge liquid crystalline (LC) graphene oxide (GO) sheets (>20 um) in water and a wide range of organic solvents. • Forms composites with superior mechanical performances. • Can be reduced by mild methods to graphene. • Can be wet-spun into fibres. Expanded graphite Graphite LC-GOaq CCG sheets from LC-GO rapid heating oxidation reduction solid state SEMs of GO fibre
- 31. 31 Spraying coating Ink-jet printing Fiber spinning Extrusion printing of 2D and 3D structures Screen printing 1 layer 2 layers 10 layers Examples of The Fabrication of LC-GO 1. Jalili, R. et al. Scalable One-Step Wet-Spinning of Graphene Fibers and Yarns from Liquid Crystalline Dispersions of Graphene Oxide: Towards Multifunctional Textiles. Adv. Funct. Mater. 2013, Ahead of Print. 2. Jalili, R. et al. Organic Solvent-Based Graphene Oxide Liquid Crystals: A Facile Route toward the Next Generation of Self-Assembled Layer-by-Layer Multifunctional 3D Architectures. ACS Nano 2013, 7, 3981- 3990.
- 32. Materials for CO2 reduction? + Doctor blade / reel-to-reel printing Catalytic films / fibres for CO2 reduction
- 33. Summary Multifunctional molecular materials (reaction centres) such as porphyrins are essential for creating energy devices. Also need nanostructured materials like graphene. Controlled placement of the reaction centres will be the key to more efficient energy devices.
- 34. 34 Acknowledgements $ FUNDING $ Australian Research Council (Discovery and CoE) Cooperative Research Centre for Polymers Prof Keith Gordon Ms Penny Walsh Mr John Earles Mr Sam Lind Ms Stasi Elliott Prof Michael Grätzel Dr Mohammad K. Nazeeruddin Dr Robin Humphry-Baker Dr Qing Wang Dr Lukas Schmidt-Mende Dr Henry Snaith Shinshu University Dr Shogo Mori Mr Kenji Sunahara Mr Masanori Miyashita AIST Dr Ryuzi Katoh Dr Akihiro Furube Dr Luchao Du Cooperative Research Centre for Polymers Prof Dermot Diamond Dr Robert Byrne Dr Michele Zanoni Dr Larisa Florea Mr Gerry Triani Dr Mike James Dr Jeremy Yunes Prof Gordon Wallace Dr Attila Mozer Dr Pawel Wagner Dr Ying Dong Dr Sanjeev Gambhir Dr Klaudia Wagner Dr Jun Chen Dr Amy Ballantyne Dr Robert Breukers Dr Matt Griffiths Mr Tim Buchhorn Mr Joseph Giorgio Mr Nicholas Roach Mr Rhys Mitchell Mr Chris Hobbs Prof Les Dutton Dr Chris Moser Dr Goutham Kodali Dr Bodhana Discher
- 35. 35 Thank you!
Editor's Notes
- Some of the benzoic acid derivatised monoporphyrins that were syntheised and tested included…
- In the 4th millennium B.C., during the Neolithic Age in southeastern Europe, the Mariţa culture used graphite in a ceramic paint for decorating pottery.[21] Some time before 1565 (some sources say as early as 1500), an enormous deposit of graphite was discovered on the approach to Grey Knotts from the hamlet of Seathwaite in Borrowdale parish, Cumbria, England, which the locals found very useful for marking sheep.[22][23] During the reign of Elizabeth 1 (1533–1603), Borrowdale graphite was used as a refractory material to line moulds for cannonballs, resulting in rounder, smoother balls that could be fired farther, contributing to the strength of the English navy. This particular deposit of graphite was extremely pure and soft, and could easily be broken into sticks. Because of its military importance, this unique mine and its production were strictly controlled by the Crown.