GraphTED - graphene nanocomposite materials for thermoelectric devices
Lead Research Organisation:
University of Manchester
Department Name: Materials
Abstract
The Seebeck effect is a thermoelectric effect whereby a temperature gradient across a material is converted to a voltage,
which can be exploited for power generation. The growing concern over fossil fuels and carbon emissions has led to
detailed reviews of all aspects of energy generation and routes to reduce consumption. Thermoelectric (TE) technology,
utilising the direct conversion of waste heat into electric power, has emerged as a serious contender, particular for
automotive and engine related applications. Thermoelectric power modules employ multiple pairs of n-type and p-type TE
materials. Traditional metallic TE materials (such as Bi2Te3 and PbTe), available for 50 years, are not well suited to high
temperature applications since they are prone to vaporization, surface oxidation, and decomposition. In addition many are
toxic. Si-Ge alloys are also well established, with good TE performance at temperatures up to 1200K but the cost per watt
can be up to 10x that of conventional materials. In the last decade oxide thermoelectrics have emerged as promising TE
candidates, particularly perovskites (n-type) and layered cobaltites (e.g. p-type Ca3Co4O9) because of their flexible
structure, high temperature stability and encouraging ZT values, but they are not yet commercially viable. Thus this
investigation is concerned with improving the thermoelectric properties of oxide thermoelectrics, specifically Strontium
Titanate (n-type) and Bismuth Strontium Cobaltite (p-type).
The conversion efficiency of thermoelectric materials is characterised by the figure of merit ZT (where T is temperature); ZT
should be as high as possible. To maximise the Z value requires a high Seebeck coefficient (S), coupled with small thermal
conductivity and high electrical conductivity. In principle electrical conductivity can be adjusted by changes in cation/anion
composition. The greater challenge is to concurrently reduce thermal conductivity. However in oxide ceramics the lattice
conductivity dominates thermal transport since phonons are the main carriers of heat. This affords the basis for a range of
strategies for reducing heat conduction; essentially microstructural engineering to increase phonon scattering. By
introducing small pieces of graphene into the oxide it is possible to produce composites which have reduced thermal
conductivity and increased electrical conductivity. In this way the ZT characteristics of both Strontium Titanate (n-type) and
Bismuth Strontium Cobaltite (p-type) can be enhanced. We will prepare composites of the two oxides, determine their
structures, their phase content and thermoelectric properties. After validation we will construct thermoelectric modules
using the p-type and n-type composites which will be evaluated in commercially-relevant test environments.
which can be exploited for power generation. The growing concern over fossil fuels and carbon emissions has led to
detailed reviews of all aspects of energy generation and routes to reduce consumption. Thermoelectric (TE) technology,
utilising the direct conversion of waste heat into electric power, has emerged as a serious contender, particular for
automotive and engine related applications. Thermoelectric power modules employ multiple pairs of n-type and p-type TE
materials. Traditional metallic TE materials (such as Bi2Te3 and PbTe), available for 50 years, are not well suited to high
temperature applications since they are prone to vaporization, surface oxidation, and decomposition. In addition many are
toxic. Si-Ge alloys are also well established, with good TE performance at temperatures up to 1200K but the cost per watt
can be up to 10x that of conventional materials. In the last decade oxide thermoelectrics have emerged as promising TE
candidates, particularly perovskites (n-type) and layered cobaltites (e.g. p-type Ca3Co4O9) because of their flexible
structure, high temperature stability and encouraging ZT values, but they are not yet commercially viable. Thus this
investigation is concerned with improving the thermoelectric properties of oxide thermoelectrics, specifically Strontium
Titanate (n-type) and Bismuth Strontium Cobaltite (p-type).
The conversion efficiency of thermoelectric materials is characterised by the figure of merit ZT (where T is temperature); ZT
should be as high as possible. To maximise the Z value requires a high Seebeck coefficient (S), coupled with small thermal
conductivity and high electrical conductivity. In principle electrical conductivity can be adjusted by changes in cation/anion
composition. The greater challenge is to concurrently reduce thermal conductivity. However in oxide ceramics the lattice
conductivity dominates thermal transport since phonons are the main carriers of heat. This affords the basis for a range of
strategies for reducing heat conduction; essentially microstructural engineering to increase phonon scattering. By
introducing small pieces of graphene into the oxide it is possible to produce composites which have reduced thermal
conductivity and increased electrical conductivity. In this way the ZT characteristics of both Strontium Titanate (n-type) and
Bismuth Strontium Cobaltite (p-type) can be enhanced. We will prepare composites of the two oxides, determine their
structures, their phase content and thermoelectric properties. After validation we will construct thermoelectric modules
using the p-type and n-type composites which will be evaluated in commercially-relevant test environments.
Planned Impact
The work will provide a foundation for the development and exploitation of high performance thermoelectric oxide-graphene
composites to generate energy via waste heat. The beneficiaries in the commercial sector are threefold: (i) ceramic
manufacturers who will have new products, (ii) producers of energy management devices who will be able to develop new products for new low and high temperature markets, and (iii) users of thermoelectric modules, such as motor
manufacturers, generating energy from waste heat. Policy makes will benefit from the research by knowledge of
developments of environmentally friendly methods of energy generation and a way to help reduce the use of fossil fuels.
There will be opportunities for museums with exhibits highlighting the principles of thermoelectric power generation and
applications from automobiles to domestic environments. To the wider public there will be environmental benefits of utilising
oxides in place toxic metal thermoelectrics and from the generation of energy from waste heat, leading to improved fuel
consumption for automobiles and economic benefit to individuals and the UK.
The research has the potential to impact the wealth and the economic competitiveness of the UK by the development of
enhanced thermoelectric materials and power modules. For UK companies there will be new opportunities and new
markets in the production of ceramics, the development of energy management systems, and exploitation of energy
generation systems. All companies in the supply chain should become more competitive. With generation of power from
waste heat in the automobile and other sectors there will be improved fuel consumption and the potential for reduction of
imported oil to the UK, giving additional economic benefits. New thermoelectric power modules should be realised within 2-
5 years, bringing benefits to companies in the supply chain within 3-7 years. The wider benefits of effective power
generation and potential reduction of oil consumption should come within 5-10 years.
The researchers working on the project will gain specialist transferable skills in experimental design, materials fabrication,
microstructural and functional property characterisation techniques together with skills in report writing and critical analysis
that will be of great value in future employment.
Non-confidential scientific and technological findings will be disseminated to the academic and industrial communities via
presentations at major international conferences and high impact scientific publications. With our industrial collaborator we
will protect and exploit IP through the University of Manchester Technology Transfer Unit.
Our industrial collaborator ETL (specialist in Energy Management) has the necessary specialist expertise to develop test
modules and evaluate the new materials. The Manchester applicants (R Freer and I Kinloch) have significant experience of
developing and investigating structure-property relationships in functional materials, including thermoelectric materials.
With our industrial collaborators we have the necessary expertise and facilities to successfully undertake the programme of
work.
composites to generate energy via waste heat. The beneficiaries in the commercial sector are threefold: (i) ceramic
manufacturers who will have new products, (ii) producers of energy management devices who will be able to develop new products for new low and high temperature markets, and (iii) users of thermoelectric modules, such as motor
manufacturers, generating energy from waste heat. Policy makes will benefit from the research by knowledge of
developments of environmentally friendly methods of energy generation and a way to help reduce the use of fossil fuels.
There will be opportunities for museums with exhibits highlighting the principles of thermoelectric power generation and
applications from automobiles to domestic environments. To the wider public there will be environmental benefits of utilising
oxides in place toxic metal thermoelectrics and from the generation of energy from waste heat, leading to improved fuel
consumption for automobiles and economic benefit to individuals and the UK.
The research has the potential to impact the wealth and the economic competitiveness of the UK by the development of
enhanced thermoelectric materials and power modules. For UK companies there will be new opportunities and new
markets in the production of ceramics, the development of energy management systems, and exploitation of energy
generation systems. All companies in the supply chain should become more competitive. With generation of power from
waste heat in the automobile and other sectors there will be improved fuel consumption and the potential for reduction of
imported oil to the UK, giving additional economic benefits. New thermoelectric power modules should be realised within 2-
5 years, bringing benefits to companies in the supply chain within 3-7 years. The wider benefits of effective power
generation and potential reduction of oil consumption should come within 5-10 years.
The researchers working on the project will gain specialist transferable skills in experimental design, materials fabrication,
microstructural and functional property characterisation techniques together with skills in report writing and critical analysis
that will be of great value in future employment.
Non-confidential scientific and technological findings will be disseminated to the academic and industrial communities via
presentations at major international conferences and high impact scientific publications. With our industrial collaborator we
will protect and exploit IP through the University of Manchester Technology Transfer Unit.
Our industrial collaborator ETL (specialist in Energy Management) has the necessary specialist expertise to develop test
modules and evaluate the new materials. The Manchester applicants (R Freer and I Kinloch) have significant experience of
developing and investigating structure-property relationships in functional materials, including thermoelectric materials.
With our industrial collaborators we have the necessary expertise and facilities to successfully undertake the programme of
work.
People |
ORCID iD |
Robert Freer (Principal Investigator) | |
Ian Kinloch (Co-Investigator) |
Publications
Azough F
(2017)
Concurrent La and A-Site Vacancy Doping Modulates the Thermoelectric Response of SrTiO3: Experimental and Computational Evidence.
in ACS applied materials & interfaces
Azough F
(2019)
Self-Nanostructuring in SrTiO3: A Novel Strategy for Enhancement of Thermoelectric Response in Oxides.
in ACS applied materials & interfaces
Ekren D
(2019)
Enhancing the thermoelectric properties of Sr1- xPr2 x/3? x/3TiO3± d through control of crystal structure and microstructure.
in Philosophical transactions. Series A, Mathematical, physical, and engineering sciences
Ekren D
(2018)
Enhancing the thermoelectric power factor of Sr 0.9 Nd 0.1 TiO 3 through control of the nanostructure and microstructure
in Journal of Materials Chemistry A
Ekren D
(2020)
Energy Storage and Conversion Materials
Freer R
(2020)
Realising the potential of thermoelectric technology: a Roadmap
in Journal of Materials Chemistry C
Freer R
(2022)
Key properties of inorganic thermoelectric materials-tables (version 1)
in Journal of Physics: Energy
Kepaptsoglou D
(2018)
Prospects for Engineering Thermoelectric Properties in La1/3NbO3 Ceramics Revealed via Atomic-Level Characterization and Modeling.
in Inorganic chemistry
Lin Y
(2015)
Thermoelectric Power Generation from Lanthanum Strontium Titanium Oxide at Room Temperature through the Addition of Graphene.
in ACS applied materials & interfaces
Lin Y
(2020)
Graphene/Strontium Titanate: Approaching Single Crystal-Like Charge Transport in Polycrystalline Oxide Perovskite Nanocomposites through Grain Boundary Engineering
in Advanced Functional Materials
Description | New composite materials based on oxides and graphene with higher performance, and over wider temperature range than traditional oxide materials |
Exploitation Route | New thermoelectric modules for power generation, operating over wide temperature range |
Sectors | Aerospace, Defence and Marine,Energy,Transport |
Description | Routes to produce thermoelectric modules based on oxide-graphene composites. A patent was filed in 2015 - WO2014125292-A1 Thermoelectric composite material useful in thermoelectric generators comprises a metal oxide material; and graphene or modified graphene dispersed throughout the metal oxide material. This is now approved in several regions including Europe, USA, Korea and Japan. Partnerships are still being sought to exploit the IP covered. |
First Year Of Impact | 2015 |
Sector | Energy |
Impact Types | Economic |
Description | From the Indian Copper Belts to Chulhas: Affordable Thermoelectric Materials for Rural India |
Amount | £609,274 (GBP) |
Funding ID | EP/T020040/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 04/2020 |
End | 03/2022 |
Description | MISE Functional Materials Network |
Amount | £30,000 (GBP) |
Organisation | University of St Andrews |
Sector | Academic/University |
Country | United Kingdom |
Start | 05/2018 |
End | 08/2018 |
Description | UMIP |
Amount | £180,000 (GBP) |
Organisation | University of Manchester |
Sector | Academic/University |
Country | United Kingdom |
Start | 11/2018 |
End | 02/2020 |
Description | ETL |
Organisation | European Thermodynamics |
Country | United Kingdom |
Sector | Private |
PI Contribution | Development of Thermoelectric Oxides |
Collaborator Contribution | Development of Thermoelectric Oxide modules |
Impact | Patent Publication |
Start Year | 2011 |
Title | THERMOELECTRIC MATERIALS AND DEVICES COMPRISING GRAPHENE |
Description | Composite materials with thermoelectric properties and devices made from such materials are described. The thermoelectric composite material may comprise a metal oxide material and graphene or modified graphene. It has been found that the addition of graphene or modified graphene to thermoelectric metal oxide materials increases ZT. It has further been found that the ZT of the metal oxide becomes effective over a broader temperature range and at lower temperatures. |
IP Reference | WO2014125292 |
Protection | Patent granted |
Year Protection Granted | 2014 |
Licensed | No |
Impact | Follow up collaborative project with European Thermodynamics Ltd funded by EPSRC-TSB |
Description | ACerS MCARE Conference Vancouver Canada August 2018 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | ACerS MCARE International Conference on Energy Materials; 700 delegates |
Year(s) Of Engagement Activity | 2018 |
Description | Annual MASSIVE Research Workshop on Environmetally Friendly Energy Materials - Weston Super Mere UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Annual MASSIVE Research Workshop on Environmetally Friendly Energy Materials - 80 peolple attended; research presentations over two days; invited talks from industry. |
Year(s) Of Engagement Activity | 2018 |
Description | CLOSELOOP Energy Materials Workshop, Helsinki Finland November 2018 |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | CLOSELOOP Energy Materials Workshop, concerned with environmentally friendly materials, 75 delegates |
Year(s) Of Engagement Activity | 2018 |
Description | Energy Materials Network Workshop, Edinburgh, UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | One day international research workshop reviewing developments in energy materials and their applications |
Year(s) Of Engagement Activity | 2017 |
Description | European Ceramic Society conference Turin Italy |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Exchange of research activities between over 500 researchers in technical ceramics |
Year(s) Of Engagement Activity | 2019 |
URL | https://www.ecers2019.org/ |
Description | European Thermoelectric Conference lLisbon |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Talk on - The effect of stoichiometry on the crystal structure and thermoelectric properties of Bi2+xSr2Co2Oy |
Year(s) Of Engagement Activity | 2016 |
Description | India-UK Thermoelectric Workshop, India Bangalore |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Thre day international research workshop reviewing developments in thermoelectric materials and their applications. Explored possible bids for international collaboration |
Year(s) Of Engagement Activity | 2018 |
Description | International Conference on Thermoelectrics, Caen France July 2018 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | International conference thermoelectrics; 600 delegates, presentations over 5 days. |
Year(s) Of Engagement Activity | 2018 |
Description | International Thermoelectric Conference Korea |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | International conference about energy materials |
Year(s) Of Engagement Activity | 2019 |
URL | http://www.its.org/content/ict2019-38th-international-conference-thermoelectrics |
Description | International Thermoelectric Symposium, Dresden |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Talk reporting - Tungsten Bronze Barium Neodymium Titanate (Ba6-3xNd8+2xTi18O54): A new high temperature oxide thermoelectric |
Year(s) Of Engagement Activity | 2015 |
Description | MISE Functional Materials workshop Birmingham UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | MISE Functional Materials workshop; 70 delegates |
Year(s) Of Engagement Activity | 2018 |
Description | Materials Research Society Annual Meeting Arizona |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Talk reporting - Thermoelectric Graphene-Strontium Titanate composites with High ZT and Wide Operating window - to international research audience |
Year(s) Of Engagement Activity | 2016 |
Description | Novel Energy Materials Workshop - lLverpool UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Series of presentations on Novel Energy Materials - 60 people attended; Liverpool University |
Year(s) Of Engagement Activity | 2018 |
Description | PacRim International Conference Hawaii USA |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | PacRim International Conference Hawaii USA; session concerned with energy materials |
Year(s) Of Engagement Activity | 2017 |
Description | Royal Society Discussion Meeting on Energy Materials Buckinhamshire UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Royal Society Discussion Meeting on Energy Materials; 80 delegates |
Year(s) Of Engagement Activity | 2018 |
Description | Thermoelectric Materials Symposium Japan |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Talk reporting - High ZT Graphene-Strontium Titanate Thermoelectric Composites - to international audience |
Year(s) Of Engagement Activity | 2015 |
Description | Thermoelectric Network Meeting in Edinburgh UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | One day workshop on thermoelectric energy materials and devices - EPSRC Thermoelectric Network |
Year(s) Of Engagement Activity | 2018 |
Description | Thermoelectric Network Workshop, Edinburgh, UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | One day international research workshop reviewing developments in thermoelectric materials and their applications |
Year(s) Of Engagement Activity | 2018 |
URL | http://www.thermoelectricnetwork.com/home.html |
Description | Thermoelectric Network Workshop, Glasgow UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | One day workshop on progress in thermoelectric materials and their applications |
Year(s) Of Engagement Activity | 2016 |
URL | http://www.thermoelectricnetwork.com/home.html |
Description | Thermoelectric Network Workshop, Manchester, UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Two day international research workshop reviewing developments in thermoelectric materials and their applications |
Year(s) Of Engagement Activity | 2017 |
URL | http://www.thermoelectricnetwork.com/home.html |
Description | Thermoelectric Network Workshop, NPL Teddington, UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | One day workshop on research developments in thermoelectrics, and one day training event on measurement techniques for thermoelectrics |
Year(s) Of Engagement Activity | 2016 |
URL | http://www.thermoelectricnetwork.com/home.html |
Description | Thermoelectric Network Workshop, Reading UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Study participants or study members |
Results and Impact | One day workshop on techniques and applications in thermoelectrics, followed by one day Trainng Event for younger workers - theme of modelling in Thermoelectrcs |
Year(s) Of Engagement Activity | 2015 |
Description | Thermoelectric Network Workshop, Southamton, UK |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Undergraduate students |
Results and Impact | One day international research workshop reviewing developments in thermoelectric materials and their applications |
Year(s) Of Engagement Activity | 2017 |
Description | Thermoelectric Network Workshop, loughborough UK |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Series of presentations by specialist on thermoelectrics concerned with engineering applications. Training event for postgraduate students and young researchers concerned with use of thermoelectrics for automotive applications |
Year(s) Of Engagement Activity | 2015 |
URL | http://www.thermoelectricnetwork.com/home.html |
Description | Thermoelectric Network meeting London UK |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Thermoelectric network meeting for exchange of reseach information between researchers in energy materials |
Year(s) Of Engagement Activity | 2019 |
URL | http://www.thermoelectricnetwork.com/past-meetings-2019.html |
Description | Virtual presentation to MISE Network |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Presentation on use of interfaces to control properties of oxide thermoelectrics |
Year(s) Of Engagement Activity | 2021 |