Multiscale in-situ characterisation of degradation and reactivity in solid oxide fuel cells
Lead Research Organisation:
Imperial College London
Department Name: Materials
Abstract
As alternative and low carbon energy technologies are of increasing international importance there is considerable debate as to the most appropriate technology solutions for power generation. For a distrubted generation scenario with power output in the range of kW to MW the solid oxide fuel cell (SOFC) is a leading contender, with development undertaken by many international companies. One of the areas of concern with new technologies is the lifetime of the device and as SOFCs operate at elevated temperatures any degradation of components may be accelerated. Due to the complexity of these devices there has been limited scope to analyse the operation of the SOFC in-situ, and from this determine mechanistic information on degradation processes. It is the aim of this proposal to tackle this challenge.Degradation and reactivity of solid oxide fuel cells may be characterised by processes occuring on a variety of length scales, from chemical reactivity and diffusion processes on the atomic scale through surface chemsitry, stress in functional layers and thermal management over mm and cm. Each of the processes contributes to the overall cell degradation, but may evolve differently depending on the functional component concerned - hence anode and cathode processes will be significantly different. As these are complex devices characterising these processes and the origin of them is challenging and currently results from post-mortem analysis. Whilst this is one route to understanding the failure of devices, an in-situ characterisation under operating conditions will provide detailed direct understanding. Our approach is to develop a combination of complimentary techniques that will allow detailed study of device operation using diffraction, spectroscopy, ion scattering, modelling and emissivity measurements. We will tackle known degradation issues in fuel cells including carbonate and Cr poisoning of cathodes, carbon formation on anodes and electrode delamination and will interact strongly with the UK Supergen Fuel Cells programme. As a result of this programme we will be able to inform industrial partners of mitigation strategies to minimise device degradation and use this information in development of new materials.
Planned Impact
In this project our aim is to develop robust in-situ methods for the characterisation and testing of intermediate temperature solid oxide fuel cells with the overall objective of understanding degradation mechanisms. As discussed in the proposal degradation of fuel cell components is an issue of immense significance to commercial developers of fuel cells and hence the advances resulting from this project are likely to impact upon fuel cell development and commercialisation worldwide. Of course with the current requirement to produce energy with low carbon emissions and environmental impact, any advances in understanding of processes that will ultimately accelerate deployment of low carbon energy production will be welcomed. The international interest in this work is highlighted by the support from groups around Europe, the US and also from fuel cell developers. We also note that this crucial work supports the UK national fuel cells programme (Supergen -www.supergenfuelcells.co.uk) in which all of the investigators are participants, and addresses an aspect which is not part of the research programme. Supergen also includes a number of fuel cell companies thus ensuring that the project team have excellent opportunities to maximise the impact of this research. To ensure that the project is successful the project team will meet regularly (at least every 6 months) and will be integrated within the national fuel cells programme, ensuring significant input from the commercial sector.It is our view that the work proposed in this proposal could have significant commercial impact and we will ensure that the necessary intellectual property (IP) is protected by patents, filed through the appropriate technology transfer office of the academic partner institutions. At Imperial College this will be Imperial Innovations who have considerable experience across many technology sectors including in fuel cell technology. St Andrews, UCL and Newcastle have analogous bodies. In cases where the research activities are collaborations across two or more institutions agreements regarding exploitation of any IP generated will be produced prior to the start of the project. Within the project team there are several investigators with a track record of development and exploitation of IP (Profs. Brandon, Kilner & Irvine) and jointly they will be responsible for ensuring that an appropriate IP strategy is followed. Each of these investigators have founded and developed a fuel cell company, with Brandon and Kilner forming Ceres Power, now a ~£60M Imperial spin out company. Once IP is protected we will engage in discussions with potential industry partners under appropriate non-disclosure agreements ensuring that all IP is appropriately protected. We will endeavour to ensure that the project team (Imperial, UCL, Newcastle and St Andrews) will be in a position to exploit the research results and innovations through the respective technology transfer offices and partnership(s) with companies and/or their supply chain. After any patent filing, the non-confidential outputs from the project will be widely disseminated via peer reviewed publication, presentations at major international conferences such as Solid State Ionics, Grove Fuel Cell Symposium, Materials Research Society Symposia, Electrochemical Society Meetings (e.g. SOFC XII) and the UK Fuel Cell and Hydrogen network of which Imperial is an active participant.
Organisations
- Imperial College London (Lead Research Organisation)
- University of Rennes 1 (Collaboration)
- Kyushu University (Collaboration)
- Marcoule Institute for Separative Chemistry (ICSM) (Collaboration)
- Ceres Power Ltd (Project Partner)
- University of Castilla-La Mancha (Project Partner)
- National Physical Laboratory NPL (Project Partner)
Publications

Bahout M
(2015)
Stability of NdBaCo 2-x Mn x O 5+d (x = 0, 0.5) layered perovskites under humid conditions investigated by high-temperature in situ neutron powder diffraction
in Journal of Materials Chemistry A

Boldrin D
(2017)
Recovery of the intrinsic thermoelectric properties of CaMn0.98Nb0.02O3 in 2-terminal geometry using Ag infiltration
in Acta Materialia

Cooper S
(2015)
Multi Length-Scale Quantification of Hierarchical Microstructure in Designed Microtubular SOFC Electrodes
in ECS Transactions

Cooper S
(2016)
TauFactor: An open-source application for calculating tortuosity factors from tomographic data
in SoftwareX

Cooper S
(2014)
Image based modelling of microstructural heterogeneity in LiFePO 4 electrodes for Li-ion batteries
in Journal of Power Sources

Cooper S
(2013)
Microstructural Analysis of an LSCF Cathode Using In Situ Tomography and Simulation
in ECS Transactions

Cooper Samuel J.
(2016)
Quantifying the transport properties of solid oxide fuel cell electrodes

Cooper SJ
(2017)
Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.
in Physical chemistry chemical physics : PCCP

Duboviks V
(2013)
In-Operando Raman Spectroscopy Study of Passivation Effects on Ni-CGO Electrodes in CO 2 Electrolysis Conditions
in ECS Transactions

Duboviks V
(2014)
A Raman spectroscopic study of the carbon deposition mechanism on Ni/CGO electrodes during CO/CO2 electrolysis.
in Physical chemistry chemical physics : PCCP
Description | New insights have been gained into the processes by which solid oxide fuel cells (SOFCs) degrade during operation, and a combination of new techniques and collaborations developed to utilise these findings. New software has been developed to fit diffusion data, and the application of ion beam techniques to characterise surface chemistry implemented. Additional combined spectroscopy and diffraction measurements have been developed for operating SOFCs, as well as tomographic approaches to probe the microstructure of tubular cells. |
Exploitation Route | Techniques are currently being used by CeresPower who are now partners in an Impact Acceleration project hosted at Imperial, and who are also employing a graduated researcher part-time. CeresPower are also supporting a further successful Platform grant application. One of the major findings has been in the development of the TraceX software package for analysis of isotopic exchange data. This has been made available to the academic community. It has been adopted as the standard for fitting diffusion data and has received considerable international interest. It also allowed, for the first time, the analysis of back-diffusion data. |
Sectors | Energy |
Description | One of the PhD students (Cooper) was embedded with an industry partner (Ceres Power) to transfer knowledge directly to them. Subsequently Dr Cooper secured a position as Senior Lecturer at Imperial College London, and is now supervising his own PhD student, on a CASE award supported by Ceres Power. A second PhD student (Niania) has also engaged with Ceres Power through a pathways to impact (PtI) award and the new insights developed are aiding the company to accelerate commercialisation of their technology. A further PtI award with Ceres Power to probe composition of cathode materials resulted from our surface studies of oxides, supporting one PDRA (Dr A Berenov) and these interactions have led to further engagement with Ceres Power in which they fully funded a PhD student (supervised by S Skinner) who was aligned with the EPSRC CDT in Advanced Materials Characterisation. Further discussions with the sponsor led to their support for a new Centre for Doctoral Training application (2018) which was successful. There has been continued collaboration with Ceres Power that has led to the direct support for Prof. Skinner in a Royal Academy of Engineering Research Chair application. Ceres, as industrial sponsor has committed £750k in direct contribution and a matching in-kind contribution, highlighting the importance of this work. This funding application was also successful with Prof Skinner being awarded a Research Chair in March 2021. We have also been successful in applying our knowledge to related fields and in securing partnerships with new industry partners, including BP-ICAM and LiNa Energy Ltd. |
First Year Of Impact | 2017 |
Sector | Energy |
Impact Types | Societal Economic |
Description | Armourers and Brasiers PhD Travel Award |
Amount | £750 (GBP) |
Organisation | Armourers & Brasiers |
Sector | Private |
Country | United Kingdom |
Start |
Description | EPSRC Pathways to Impact |
Amount | £67,162 (GBP) |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 03/2015 |
End | 10/2016 |
Description | EPSRC Pathways to Impact |
Amount | £65,000 (GBP) |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 05/2016 |
End | 04/2017 |
Description | EPSRC Platform Grant |
Amount | £1,304,889 (GBP) |
Funding ID | EP/R002010/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 09/2017 |
End | 09/2022 |
Description | EPSRC Responsive |
Amount | £1,076,043 (GBP) |
Funding ID | EP/M01412/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 03/2015 |
End | 03/2019 |
Description | EPSRC-JSPS Core to Core |
Amount | £1,001,181 (GBP) |
Funding ID | EP/P026478/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 06/2017 |
End | 07/2022 |
Description | Imperial College Junior Research Fellowship - Dr Na Ni |
Amount | £150,000 (GBP) |
Organisation | Imperial College London |
Sector | Academic/University |
Country | United Kingdom |
Start | 07/2014 |
End | 08/2017 |
Description | Marie Curie Scheme |
Amount | £160,000 (GBP) |
Organisation | European Commission |
Sector | Public |
Country | European Union (EU) |
Start | 03/2017 |
End | 04/2019 |
Description | STFC Early Career Grant |
Amount | £250 (GBP) |
Organisation | Science and Technologies Facilities Council (STFC) |
Sector | Public |
Country | United Kingdom |
Start |
Title | TauFactor |
Description | A Matlab application to efficiently calculate tortuosity factors form Image data. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2016 |
Provided To Others? | Yes |
Impact | The app has been downloaded and the publication relating to it cited 41 times, |
URL | https://sourceforge.net/projects/taufactor/ |
Title | TraceX software |
Description | A new Matlab routine to fit isotopic exchange data, including back diffusion. Specifically developed to use time-of-flight secondary ion mass spectrometry data. |
Type Of Material | Improvements to research infrastructure |
Year Produced | 2015 |
Provided To Others? | Yes |
Impact | Several papers produced using this technique, plus formed significant part of PhD thesis. Also paper in progress describing the methods, as well as having presented this at an international conference. |
URL | https://sourceforge.net/projects/trace-x/ |
Description | Double perovskites - Mona |
Organisation | University of Rennes 1 |
Country | France |
Sector | Academic/University |
PI Contribution | Collaboration on neutron scattering studies - staffed the beam time |
Collaborator Contribution | Partner provided samples and attended the beamtime. |
Impact | Open access paper published and further works in progress. |
Start Year | 2014 |
Description | Environmental SEM |
Organisation | Marcoule Institute for Separative Chemistry (ICSM) |
Country | France |
Sector | Charity/Non Profit |
PI Contribution | Provided samples, student visited, drafted paper and presented work at conference |
Collaborator Contribution | Provided access to ESEM instrument, assisted with interpretation. |
Impact | Papers as highlighted in the publications list. |
Start Year | 2014 |
Description | Kyushu University |
Organisation | Kyushu University |
Country | Japan |
Sector | Academic/University |
PI Contribution | Mathew Niania and John Kilner visited the lab in Japan and undertook collaborative research |
Collaborator Contribution | Partners made staff time available as well as time on the instruments (SIMS/LEIS) |
Impact | Contribution towards PhD thesis and subsequent papers |
Start Year | 2014 |
Title | TraceX Matlab App |
Description | Isotopic exchange data fitting routine for Matlab. |
Type Of Technology | Webtool/Application |
Year Produced | 2015 |
Impact | PhD thesis produced. Paper presented at international conference (Solid State Ionics 20, 2015). Papers using the routines have been published. |
URL | https://sourceforge.net/projects/trace-x/ |
Description | Interview on use of Latex - Sam Cooper |
Form Of Engagement Activity | A press release, press conference or response to a media enquiry/interview |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Short interview given at: https://www.overleaf.com/blog/189-writelatex-author-interview-sam-cooper-imperial-college-london#.VthMkCgnwdU |
Year(s) Of Engagement Activity | 2014 |
URL | https://www.overleaf.com/blog/189-writelatex-author-interview-sam-cooper-imperial-college-london#.Vt... |
Description | Invited workshop speaker |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Engaged as an international speaker in a NSF funded US-Africa workshop, highlighting and presenting opportunities to researchers in Africa (Uganda, Tanzania, Kenya etc) to partner with US and European researchers. |
Year(s) Of Engagement Activity | 2016 |
URL | http://juami.ms.northwestern.edu/index.html |
Description | Sam Cooper - 3 minute thesis competition |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | Dissemination of the content of a tomography PhD thesis |
Year(s) Of Engagement Activity | 2015 |
URL | https://www.youtube.com/watch?v=BtroaG3xuAA |
Description | Schools outreach visit |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Schools |
Results and Impact | Invited to participate in a schools science event |
Year(s) Of Engagement Activity | 2016 |