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Polymer-Redox Interactions Enhance Ferro/Ferricyanide Thermogalvanic Cells
Linköping University, Department of Science and Technology, Laboratory of Organic Electronics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0001-7783-6816
Linköping University, Department of Science and Technology, Laboratory of Organic Electronics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-8242-7547
Birla Inst Technol & Sci BITS, India.
Birla Inst Technol & Sci BITS, India.
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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. Vol. 36, no 58, article id e76685
Keywords [en]
aqueous solution; chemical engineering; electrolyte; materials science; polyelectrolyte; power density; redox; seebeck coefficient; thermoelectric effect; thermoelectric materials
National Category
Energy Engineering
Identifiers
URN: urn:nbn:se:liu:diva-226871DOI: 10.1002/adfm.76685ISI: 001804458100001Scopus ID: 2-s2.0-105042828597OAI: oai:DiVA.org:liu-226871DiVA, id: diva2:2093690
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
In thesis
1. Development of Novel Thermogalvanic Devices for Energy Harvesting
Open this publication in new window or tab >>Development of Novel Thermogalvanic Devices for Energy Harvesting
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
Energy harvesting, Thermogalvanic cells, Ionic thermoelectric generators, Thermogalvanic modules, Electrochemistry, Sustainability, Energiutvinning, Termogalvaniska celler, Joniska termoelektriska generatorer, Termogalvaniska moduler, Elektrokemi, Hållbarhet
National Category
Energy Systems
Identifiers
urn:nbn:se:liu:diva-227126 (URN)10.3384/9789181186383 (DOI)9789181186376 (ISBN)9789181186383 (ISBN)
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

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