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Development of Novel Thermogalvanic Devices for Energy Harvesting
Linköping University, Department of Science and Technology, Laboratory of Organic Electronics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0001-7783-6816
2026 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The energy matrix corresponds to all sources of energy necessary to supply electricity, heat, and fuel for industrial and human activities. It is fundamental for the economic development of a country or region and highly impacts on sustainability, as it is related to available resources, energetic efficiency, and potential environmental impact of each source (fossil fuels, wind, solar, biofuels). The world’s energy matrix should be diversified and depend as little as possible on fossil fuels, to guarantee energy security, reduce emissions and promote sustainability.

A sustainable energetic society also depends on finding ways of storing the energy safely and efficiently and searching for alternative ways of harvesting energy. Thermoelectric devices are attractive because they can directly convert a heat flux into electricity due to the so-called Seebeck effect. Thermoelectric generators that convert low-grade waste heat (typically below 100°C) into electricity are of particular interest, because such heat sources are easily available on Earth, from data centres, industry, solar radiation, and the human body.

Thermogalvanic cells (TGCs) are unique thermal energy harvesters that can be operated at room temperature, suitable for low-grade heat harvesting. They typically have relatively high Seebeck coefficient values and can generate continuous power output under temperature gradient. This thesis’ purpose was to develop novel thermogalvanic cells towards practical applications, including improving Seebeck coefficient and power output, and establishing manufacture protypes for thermogalvanic modules.

The works presented in this PhD thesis consist in (i) the understanding and improving the functioning of activated carbon electrodes in a potassium ferro/ferricyanide based thermogalvanic cell. (ii) Large scale manufacturing of fully printed thermogalvanic modules. (iii) Investigating the impact of polyelectrolyte on improving the Seebeck coefficient, power output and charge transfer in TGCs. (iv) Proposing a TGC based on non-volatile organic electrolyte based on copper and TEMPO active redox species. (v) Developing a redox reaction enabled ionic thermoelectric generator, with constant power generation and high thermovoltage.

Abstract [sv]

Energimatrisen omfattar alla energikällor som krävs för att tillhandahålla elektricitet, värme och bränsle för industriella och mänskliga aktiviteter. Den utgör en grundläggande förutsättning för den ekonomiska utvecklingen i ett land eller en region och har stor betydelse för hållbarheten, eftersom den är kopplad till tillgängliga resurser, energieffektivitet och den potentiella miljöpåverkan från varje energikälla (fossila bränslen, vind, sol, biobränslen). En global energimatrix bör vara diversifierad och så oberoende av fossila bränslen som möjligt för att säkerställa energitrygghet, minska utsläpp och främja hållbar utveckling.

Ett hållbart energisamhälle är också beroende av att hitta sätt att lagra energi på ett säkert och effektivt sätt samt att söka alternativa metoder för energiutvinning. Termoelektriska enheter är attraktiva eftersom de direkt kan omvandla ett värmeflöde till elektricitet genom den så kallade Seebeckeffekten. Särskilt intressanta är termoelektriska generatorer som omvandlar låggradig spillvärme (vanligen under 100°C) till elektricitet, eftersom sådana värmekällor är lättillgängliga på jorden, exempelvis från datacenter, industriella processer, solstrålning och människokroppen.

Termogalvaniska celler (TGC) är unika system för utvinning av termisk energi som kan drivas vid rumstemperatur och lämpar sig väl för att ta tillvara låggradig värme. De har vanligtvis relativt höga värden på Seebeckkoefficienten och kan generera en kontinuerlig uteffekt när de utsätts för en temperaturgradient. Syftet med denna avhandling var att utveckla nya termogalvaniska celler för praktiska tillämpningar, inklusive att förbättra Seebeckkoefficienten och effektuttaget samt att etablera tillverkningsprototyper för termogalvaniska moduler.

Arbetet som presenteras i denna doktorsavhandling omfattar: (i) förståelse och förbättring av aktiverade kolelektroders funktion i termogalvaniska celler baserade på kalium ferro-/ferricyanid, (ii) storskalig tillverkning av fullt tryckta termogalvaniska moduler, (iii) undersökning av polyelektrolyters inverkan på Seebeck-koefficient, effektutgång och laddningstransport i TGCs, (iv) utveckling av en TGC baserad på en icke-flyktig organisk elektrolyt med koppar- och TEMPO-baserade redoxaktiva arter, samt (v) framtagning av en jonisk termoelektrisk generator möjliggjord av redoxreaktioner, med konstant effektgenerering och hög termospänning.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2026. , p. 90
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 2537
Keywords [en]
Energy harvesting, Thermogalvanic cells, Ionic thermoelectric generators, Thermogalvanic modules, Electrochemistry, Sustainability
Keywords [sv]
Energiutvinning, Termogalvaniska celler, Joniska termoelektriska generatorer, Termogalvaniska moduler, Elektrokemi, Hållbarhet
National Category
Energy Systems
Identifiers
URN: urn:nbn:se:liu:diva-227126DOI: 10.3384/9789181186383ISBN: 9789181186376 (print)ISBN: 9789181186383 (electronic)OAI: oai:DiVA.org:liu-227126DiVA, id: diva2:2095496
Public defence
2026-10-15, K4, Kåkenhus, Campus Norrköping, Norrköping, 10:00 (English)
Opponent
Supervisors
Available from: 2026-08-26 Created: 2026-08-26 Last updated: 2026-08-26Bibliographically approved
List of papers
1. Printable Carbon-Based Thermogalvanic Cells
Open this publication in new window or tab >>Printable Carbon-Based Thermogalvanic Cells
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2025 (English)In: Advanced Energy & Sustainability Research, E-ISSN 2699-9412, Vol. 6, no 8, article id 2400428Article in journal (Refereed) Published
Abstract [en]

Thermogalvanic cells (TGCs) can convert low-grade heat directly into electricity through reversible redox reactions induced by temperature gradient. As a unique member of the thermoelectric device family, TGCs provide advantages such as cost-effective and sustainable materials, a relatively high Seebeck coefficient, and the ability to generate continuous output power. To date, the challenge toward commercializing TGCs lies in developing functional electrode materials that can be produced on a large scale. Herein, the performance of printable activated carbon (AC) as the electrode in TGC is investigated. The multilayer printing of the AC electrodes provides increasing capacitance and improves the maximum output power of the TGC. This is mainly due to the decrease in the device's total resistance thanks to the large surface area of thick AC electrodes. The advanced understanding of the interface between the printed electrode and electrolyte paves the road toward printable and sustainable TGC.

Place, publisher, year, edition, pages
WILEY, 2025
Keywords
activated carbon; electron transfer; energy harvesting; printed electrodes; redox electrolytes; sustainability; thermogalvanic cells
National Category
Other Chemical Engineering
Identifiers
urn:nbn:se:liu:diva-212348 (URN)10.1002/aesr.202400428 (DOI)001434055400001 ()2-s2.0-85218794843 (Scopus ID)
Note

Funding Agencies|EU Commission under the project Metatherm [101058284]; Swedish Research Council [2024-04196, 2020-04210]; AForsk Foundation; Advanced Functional Materials Center at Linkoeping University

Available from: 2025-03-20 Created: 2025-03-20 Last updated: 2026-08-26
2. Fully Printed Thermogalvanic Modules for Low-Grade Energy Harvesting
Open this publication in new window or tab >>Fully Printed Thermogalvanic Modules for Low-Grade Energy Harvesting
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2025 (English)In: ACS Applied Energy Materials, E-ISSN 2574-0962, Vol. 8, no 17, p. 12868-12877Article in journal (Refereed) Published
Abstract [en]

Thermogalvanic cells offer a promising route for harvesting low-grade heat by utilizing temperature-dependent redox reactions at spatially separated electrodes. Their potential for low-cost, flexible, and sustainable energy conversion makes them attractive for scalable applications; however, practical implementation is limited by challenges in modular integration and manufacturability. Here, we report the development of a fully printed thermogalvanic module (TGM) that integrates screen-printed hybrid current collectors, activated carbon-based electrodes, an adhesive sealing layer, and a laser-drilled spacer. This fully additive and scalable fabrication strategy enables the precise assembly of complex architectures without traditional stacking or wiring. The resulting 36-cell TGM, employing widely available aqueous electrolytes, demonstrates a reproducible thermopower of 38 mV K-1 and a peak output power of 9 mu W under a modest 14 K temperature difference. This work demonstrates a practical pathway toward large-area printed thermogalvanic systems for ambient heat harvesting and paves the way for future integration into flexible and wearable energy platforms.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2025
Keywords
low-grade thermal energy harvesting; screen-printing; thermogalvanic module; scalability; sustainability; thermogalvanic cell
National Category
Energy Systems
Identifiers
urn:nbn:se:liu:diva-217492 (URN)10.1021/acsaem.5c02080 (DOI)001557025300001 ()40937101 (PubMedID)
Note

Funding Agencies|EU commission [101058284]; Swedish Research Council [2024-04196, 2020-04210]; The aForsk Foundation and the Advanced Functional Materials Center at Linkoping University; Swedish Research Council [2020-04210, 2024-04196] Funding Source: Swedish Research Council; Horizon Europe - Pillar III [101058284] Funding Source: Horizon Europe - Pillar III

Available from: 2025-09-09 Created: 2025-09-09 Last updated: 2026-08-26
3. Polymer-Redox Interactions Enhance Ferro/Ferricyanide Thermogalvanic Cells
Open this publication in new window or tab >>Polymer-Redox Interactions Enhance Ferro/Ferricyanide Thermogalvanic Cells
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2026 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 36, no 58, article id e76685Article in journal (Refereed) Published
Abstract [en]

Thermogalvanic cells (TGCs) capable of converting low-grade heat into electricity offer a sustainable route for waste-energy recovery and self-powered devices. In this work, we introduce potassium polyacrylate (PAAK) as a low-cost and stable electrolyte additive that markedly enhances the performance of aqueous ferro/ferricyanide TGCs. Unlike previous polymer systems that typically form gel or quasi-solid electrolytes, our liquid electrolyte preserves freely solvated PAA- and K+ ions, enabling direct and tunable interactions between the polyanion and redox species. These interactions modify the hydration shell of the redox couple, thereby increasing the redox entropy difference and significantly improving the Seebeck coefficient. Despite a moderate increase in viscosity, an optimized concentration of 8% PAAK achieved a Seebeck coefficient of -2.2 mV K- 1 and a maximum power output twice that of the pristine electrolyte. Further device optimization yielded a normalized power density of 0.8 mW m- 2 K- 2, among the highest values reported for liquid TGCs. In the end, we discussed the principle of developing polyelectrolyte-enhanced redox electrolytes and demonstrated the feasibility. This study not only demonstrates a simple and low-cost route to enhance TGC performance but also provides new fundamental insight into how polyelectrolyte-redox interactions in solution can be exploited to tailor thermoelectric properties.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2026
Keywords
aqueous solution; chemical engineering; electrolyte; materials science; polyelectrolyte; power density; redox; seebeck coefficient; thermoelectric effect; thermoelectric materials
National Category
Energy Engineering
Identifiers
urn:nbn:se:liu:diva-226871 (URN)10.1002/adfm.76685 (DOI)001804458100001 ()2-s2.0-105042828597 (Scopus ID)
Note

Funding Agencies|Forsk Foundation; Swedish Research Council [2024-04196, 2020-04210]; EU Commission; Advanced Functional Materials Center at Linkping University; Metatherm [101058284]; Swedish Research Council [2024-04196, 2020-04210] Funding Source: Swedish Research Council

Available from: 2026-08-19 Created: 2026-08-19 Last updated: 2026-10-04
4. Thermal potential induced redox reaction enabled ionic thermoelectric generator
Open this publication in new window or tab >>Thermal potential induced redox reaction enabled ionic thermoelectric generator
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2026 (English)In: Nano Energy, ISSN 2211-2855, E-ISSN 2211-3282, Vol. 148, article id 111648Article in journal (Refereed) Published
Abstract [en]

We report an ionic thermoelectric generator (iTEG) capable of delivering continuous power and large thermal voltages under a temperature gradient. Unlike conventional thermogalvanic cells, the current in our system arises from a reversible redox reaction driven by ionic thermodiffusion-induced thermal potentials. By systematically studying electrolytes with varying thermoelectric properties, we identified that self-assembled polyethylene glycol (PEG) clusters, stabilized by alkoxide end groups, are key to enable the output current. The iTEG achieved a maximum power density of 4.2 mW m-2 with an output voltage of 100 mV under a 20 K temperature difference. These findings establish a new design principle for ionic thermoelectric devices and provide insights into charge transfer process and redox reactions at electrode interfaces, with implications for energy technologies such as ion batteries and related electrochemical systems.

Place, publisher, year, edition, pages
ELSEVIER, 2026
Keywords
Low grade heat harvesting; Electrolyte based material; Redox reaction; Polymer nano-cluster
National Category
Materials Chemistry
Identifiers
urn:nbn:se:liu:diva-220358 (URN)10.1016/j.nanoen.2025.111648 (DOI)001648806100001 ()2-s2.0-105025018506 (Scopus ID)
Note

Funding Agencies|EU commission [101058284]; Swedish Research Council [2024-04196, 2020-04210]; AForsk Foundation; Advanced Functional Materials Center at Linkoping University

Available from: 2026-01-14 Created: 2026-01-14 Last updated: 2026-08-26

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Santos Candiotto de Oliveira, Pedro

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