Boosted thermopower in aqueous thermocells through additives-induced ionic regulation for low-grade heat harvesting

Yijie Mu , Kedi Li , Kaiyu Mu , Yung-Kang Peng , Shien-Ping Feng

Energy Materials ›› 2025, Vol. 5 ›› Issue (9) : 500119

PDF
Energy Materials ›› 2025, Vol. 5 ›› Issue (9) :500119 DOI: 10.20517/energymater.2025.34
Article

Boosted thermopower in aqueous thermocells through additives-induced ionic regulation for low-grade heat harvesting

Author information +
History +
PDF

Abstract

Aqueous thermocells are promising techniques for the conversion of low-grade waste heat into electricity. However, current improvement strategies are mainly focused on single redox ions and sacrifice the electrical conductivity due to concentrated molecular additives. Herein, we report a chemical additives-regulated thermocell that introduced two ionic additives, guanidine hydrochloride and cysteamine hydrochloride, into 0.4 M ferri/ferrocyanide {[Fe(CN)6]3-/4-} electrolyte to simultaneously exert the selective crystallization effect on [Fe(CN)6]4- and the chemical regulation effect for [Fe(CN)6]3-, synergistically inducing concentration gradients of both redox ions between two electrodes, thereby improving the thermoelectric performance. Our thermocell obtained a high thermopower of 4.34 mV K-1 with comparable electrical conductivity and a Carnot-relative efficiency of 5.50% with minimal amounts of the two additives, showing adaptability to various cell orientations and thus different practical scenarios. A record-high thermopower of 9.06 mV K-1 and a Carnot-relative efficiency of 12.65% were achieved by adopting optimized concentrations of two additives under cold-over-hot orientation. A 20-unit module was developed to directly power various electronics, demonstrating its feasibility for low-grade heat harvesting.

Keywords

Thermocells / guanidine hydrochloride / cysteamine hydrochloride / chemical regulation

Cite this article

Download citation ▾
Yijie Mu, Kedi Li, Kaiyu Mu, Yung-Kang Peng, Shien-Ping Feng. Boosted thermopower in aqueous thermocells through additives-induced ionic regulation for low-grade heat harvesting. Energy Materials, 2025, 5(9): 500119 DOI:10.20517/energymater.2025.34

登录浏览全文

4963

注册一个新账户 忘记密码

References

[1]

Chu S.Opportunities and challenges for a sustainable energy future.Nature2012;488:294-303

[2]

Gur I,Prasher R.Searching for a better thermal battery.Science2012;335:1454-5

[3]

Gemma A.A roadmap for molecular thermoelectricity.Nat Nanotechnol2021;16:1299-301

[4]

He P,Kang H.Thermoelectricity in molecular tunnel junctions.Chem Rev2025;125:2953-3004

[5]

Reddy P,Segalman RA.Thermoelectricity in molecular junctions.Science2007;315:1568-71

[6]

Leblanc S,Scullin ML,Goodson KE.Material and manufacturing cost considerations for thermoelectrics.Renew. Sustain Energy Rev2014;32:313-27

[7]

Hao F,Tang Y.High efficiency Bi2Te3-based materials and devices for thermoelectric power generation between 100 and 300 °C.Energy Environ Sci2016;9:3120-7

[8]

Zhu B,Wang Q.Realizing record high performance in n-type Bi2Te3-based thermoelectric materials.Energy Environ Sci2020;13:2106-14

[9]

Zheng Z,Ao D.Harvesting waste heat with flexible Bi2Te3 thermoelectric thin film.Nat Sustain2023;6:180-91

[10]

Chen YX,Zhang JZ.Deviceization of high-performance and flexible Ag2Se films for electronic skin and servo rotation angle control.Nat Commun2024;15:8356 PMCID:PMC11436659

[11]

Yang D,Li M.Flexible power generators by Ag2Se thin films with record-high thermoelectric performance.Nat Commun2024;15:923 PMCID:PMC10830499

[12]

Dupont MF,Pringle JM.Thermo-electrochemical cells for waste heat harvesting - progress and perspectives.Chem Commun2017;53:6288-302

[13]

Jiao N,Macfarlane DR.Ionic liquid electrolytes for thermal energy harvesting using a cobalt redox couple.J Electrochem Soc2014;161:D3061-5

[14]

Sun S,Shi X.Advances in ionic thermoelectrics: from materials to devices.Adv Energy Mater2023;13:2203692

[15]

Lu X,Liu Z.Robust, efficient, and recoverable thermocells with zwitterion-boosted hydrogel electrolytes for energy-autonomous and wearable sensing.Angew Chem Int Ed2024;63:202405357

[16]

Ding Z,Long W.Thermoelectrics and thermocells for fire warning applications.Sci Bull2023;68:3261-77

[17]

Wang H,Xie W.Thermosensitive-CsI3-crystal-driven high-power I-/I3- thermocells.Cell Rep Phys Sci2022;3:100737

[18]

Yu B,Zeng Y.Cost-effective n-type thermocells enabled by thermosensitive crystallizations and 3D multi-structured electrodes.Nano Energy2022;93:106795

[19]

Abraham TJ,Pringle JM.High Seebeck coefficient redox ionic liquid electrolytes for thermal energy harvesting.Energy Environ Sci2013;6:2639-45

[20]

Zinovyeva V,Bonetti M.Enhanced thermoelectric power in ionic liquids.ChemElectroChem2014;1:426-30

[21]

Anari EH,Teh WX.Substituted ferrocenes and iodine as synergistic thermoelectrochemical heat harvesting redox couples in ionic liquids.Chem Commun2016;52:745-8

[22]

Lazar MA,MacFarlane DR.Enhanced thermal energy harvesting performance of a cobalt redox couple in ionic liquid-solvent mixtures.Phys Chem Chem Phys2016;18:1404-10

[23]

Zhou H,Kimizuka N.Supramolecular Thermo-electrochemical cells: enhanced thermoelectric performance by host-guest complexation and salt-induced crystallization.J Am Chem Soc2016;138:10502-7

[24]

Kim T,Lee G.High thermopower of ferri/ferrocyanide redox couple in organic-water solutions.Nano Energy2017;31:160-7

[25]

Duan J,Yu B.Aqueous thermogalvanic cells with a high Seebeck coefficient for low-grade heat harvest.Nat Commun2018;9:5146 PMCID:PMC6279834

[26]

Yu B,Cong H.Thermosensitive crystallization-boosted liquid thermocells for low-grade heat harvesting.Science2020;370:342-6

[27]

Wang Y,Xin X.In situ photocatalytically enhanced thermogalvanic cells for electricity and hydrogen production.Science2023;381:291-6

[28]

Yu B,Li J.Heat-triggered high-performance thermocells enable a self-powered forest fire alarm.J Mater Chem A2021;9:26119-26

[29]

Kraemer D.A simple differential steady-state method to measure the thermal conductivity of solid bulk materials with high accuracy.Rev Sci Instrum2014;85:025108

[30]

Jannot Y.Steady-state methods. In Thermal Properties Measurement of Materials, 1st ed.; ISTE Ltd and John Wiley & Sons, Inc., 2018; pp 83-116.

[31]

Zhang D,Ye F.Stretchable thermogalvanic hydrogel thermocell with record-high specific output power density enabled by ion-induced crystallization.Energy Environ Sci2022;15:2974-82

[32]

Liu L,Bai P.Strong tough thermogalvanic hydrogel thermocell with extraordinarily high thermoelectric performance.Adv Mater2023;35:e2300696

[33]

Elgrishi N,Mccarthy BD,Eisenhart TT.A practical beginner’s guide to cyclic voltammetry.J Chem Educ2018;95:197-206

[34]

Cui Y,Luo Z.Synthesis of cysteamine hydrochloride by high pressure acidolysis of 2-mercaptothiazoline.Asian J Chem2010;22:3221-7https://asianpubs.org/index.php/ajchem/article/view/11535 (accessed 2025-06-12).

[35]

Dénès F,Povie G.Thiyl radicals in organic synthesis.Chem Rev2014;114:2587-693

[36]

Paulsen CE.Cysteine-mediated redox signaling: chemistry, biology, and tools for discovery.Chem Rev2013;113:4633-79 PMCID:PMC4303468

[37]

Nekrassova O,Lawrence N,Jones T.The oxidation of cysteine by aqueous ferricyanide: a kinetic study using boron doped diamond electrode voltammetry.Electroanalysis14:1464-9

[38]

Romano MS,Antiohos D.Carbon nanotube - reduced graphene oxide composites for thermal energy harvesting applications.Adv Mater2013;25:6602-6

[39]

Laschuk NO,Zenkina OV.Reducing the resistance for the use of electrochemical impedance spectroscopy analysis in materials chemistry.RSC Adv2021;11:27925-36 PMCID:PMC9038008

[40]

Quickenden TI.A Review of power generation in aqueous thermogalvanic cells.J Electrochem Soc1995;142:3985

[41]

Hu R,Haram N.Harvesting waste thermal energy using a carbon-nanotube-based thermo-electrochemical cell.Nano Lett2010;10:838-46

[42]

Im H,Song H.High-efficiency electrochemical thermal energy harvester using carbon nanotube aerogel sheet electrodes.Nat Commun2016;7:10600 PMCID:PMC4742963

[43]

Qian W,Xie F.Thermo-electrochemical cells based on carbon nanotube electrodes by electrophoretic deposition.Nano-Micro Lett2016;8:240-6 PMCID:PMC6223680

[44]

Zhang L,Li N.High power density electrochemical thermocells for inexpensively harvesting low-grade thermal energy.Adv Mater2017;29:1605652

[45]

Li G,Hong G,Zhang X.High-Efficiency cryo-thermocells assembled with anisotropic holey graphene aerogel electrodes and a eutectic redox electrolyte.Adv Mater2019;31:1901403

[46]

Zhao LD,Zhang Y.Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals.Nature2014;508:373-7

[47]

Burkov AT,Novikov SV.Methods and apparatus for measuring thermopower and electrical conductivity of thermoelectric materials at high temperatures. In Thermoelectrics for power generation - a look at trends in the technology; Skipidarov, S.; Nikitin, M.; Eds.; InTech, 2016; pp 351-87

[48]

Wang H,Chen G.A brief review on measuring methods of thermal conductivity of organic and hybrid thermoelectric materials.Adv Elect Mater2019;5:1900167

[49]

Wei T,Yu J,Chen L.How to measure thermoelectric properties reliably.Joule2018;2:2183-8

[50]

Jiang L,Nandal V.Thermoelectrochemical cells based on ferricyanide/ferrocyanide/guanidinium: application and challenges.ACS Appl Mater Interfaces2022:22921-8

[51]

Zhou H,Ujita M.Advancement of electrochemical thermoelectric conversion with molecular technology.Angew Chem Int Ed2023;62:e202213449

[52]

Wang WT,Zhou N.Water- and heat-activated dynamic passivation for perovskite photovoltaics.Nature2024;632:294-300

[53]

Kang TJ,Kozlov ME.Electrical power from nanotube and graphene electrochemical thermal energy harvesters.Adv Funct Mater2012;22:477-89

PDF

68

Accesses

0

Citation

Detail

Sections
Recommended

/