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Vol. 14 (2022)

Regulating Thermogalvanic Effect and Mechanical Robustness via Redox Ions for Flexible Quasi-Solid-State Thermocells

https://doi.org/10.1007/s40820-022-00824-6
Peng Peng
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Jiaqian Zhou
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Lirong Liang
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Xuan Huang
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Haicai Lv
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Zhuoxin Liu
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China
Guangming Chen
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, People’s Republic of China

Corresponding Author: Guangming Chen

chengm@szu.edu.cn

Nano-Micro Letters, Vol. 14 (2022), Article Number: 81

Abstract

The design of power supply systems for wearable applications requires both flexibility and durability. Thermoelectrochemical cells (TECs) with large Seebeck coefficient can efficiently convert low-grade heat into electricity, thus having attracted considerable attention in recent years. Utilizing hydrogel electrolyte essentially addresses the electrolyte leakage and complicated packaging issues existing in conventional liquid-based TECs, which well satisfies the need for flexibility. Whereas, the concern of mechanical robustness to ensure stable energy output remains yet to be addressed. Herein, a flexible quasi-solid-state TEC is proposed based on the rational design of a hydrogel electrolyte, of which the thermogalvanic effect and mechanical robustness are simultaneously regulated via the multivalent ions of a redox couple. The introduced redox ions not only endow the hydrogel with excellent heat-to-electricity conversion capability, but also act as ionic crosslinks to afford a dual-crosslinked structure, resulting in reversible bonds for effective energy dissipation. The optimized TEC exhibits a high Seebeck coefficient of 1.43 mV K−1 and a significantly improved fracture toughness of 3555 J m−2, thereby can maintain a stable thermoelectrochemical performance against various harsh mechanical stimuli. This study reveals the high potential of the quasi-solid-state TEC as a flexible and durable energy supply system for wearable applications.


Highlights:


1 A redox couple is employed to fulfill the dual-function of both heat-to-electricity conversion and ionic crosslinking.
2 High thermoelectrochemical performance can be achieved at optimized redox concentration, and dual-crosslinked network ensures remarkable mechanical flexibility and robustness.
3 The hydrogel-based quasi-solid-state thermocell can provide stable energy output under harsh mechanical stress and deformations.

Keywords

Thermocells Thermoelectric Flexible energy devices Wearable applications Hydrogel electrolytes
Peng, Peng, Jiaqian Zhou, Lirong Liang, Xuan Huang, Haicai Lv, Zhuoxin Liu, and Guangming Chen. 2022. “Regulating Thermogalvanic Effect and Mechanical Robustness via Redox Ions for Flexible Quasi-Solid-State Thermocells”. Nano-Micro Letters 14 (March):81. https://doi.org/10.1007/s40820-022-00824-6.
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References
  1. I. Jeerapan, J.R. Sempionatto, J. Wang, On-body bioelectronics: wearable biofuel cells for bioenergy harvesting and self-powered biosensing. Adv. Funct. Mater. 30(29), 1906243 (2020). https://doi.org/10.1002/adfm.201906243
  2. C.G. Nunez, L. Manjakkal, R. Dahiya, Energy autonomous electronic skin. npj Flex. Electron. (2019). https://doi.org/10.1038/s41528-018-0045-x
  3. Z. Liu, D. Wang, Z. Tang, G. Liang, Q. Yang et al., A mechanically durable and device-level tough Zn-MnO2 battery with high flexibility. Energy Storage Mater. 23, 636–645 (2019). https://doi.org/10.1016/j.ensm.2019.03.007
  4. M. Salanne, B. Rotenberg, K. Naoi, K. Kaneko, P.L. Taberna et al., Efficient storage mechanisms for building better supercapacitors. Nat. Energy 1, 16070 (2016). https://doi.org/10.1038/NENERGY.2016.70
  5. Z. Shen, L. Luo, C. Li, J. Pu, J. Xie et al., Stratified zinc-binding strategy toward prolonged cycling and flexibility of aqueous fibrous zinc metal batteries. Adv. Energy Mater. 11(16), 2100214 (2021). https://doi.org/10.1002/aenm.202100214
  6. K. Zhu, P. Xue, G. Cheng, M. Wang, H. Wang et al., Thermo-managing and flame-retardant scaffolds suppressing dendritic growth and polysulfide shuttling toward high-safety lithium-sulfur batteries. Energy Storage Mater. 43, 130–142 (2021). https://doi.org/10.1016/j.ensm.2021.08.031
  7. S.A. Hashemi, S. Ramakrishna, A.G. Aberle, Recent progress in flexible-wearable solar cells for self-powered electronic devices. Energy Environ. Sci. 13(3), 685–743 (2020). https://doi.org/10.1039/c9ee03046h
  8. R.J.M. Vullers, R. Schaijk, I. Doms, C.V. Hoof, R. Mertens, Micropower energy harvesting. Solid State Electron. 53(7), 684–693 (2009). https://doi.org/10.1016/j.sse.2008.12.011
  9. R.M. Tian, Y.Q. Liu, K. Koumoto, J. Chen, Body heat powers future electronic skins. Joule 3(6), 1399–1403 (2019). https://doi.org/10.1016/j.joule.2019.03.011
  10. S.D. Kang, G.J. Snyder, Charge-transport model for conducting polymers. Nat. Mater. 16, 252–257 (2017). https://doi.org/10.1038/nmat4784
  11. J.S. Liang, T. Wang, P.F. Qiu, S.Q. Yang, C. Ming et al., Flexible thermoelectrics: from silver chalcogenides to full-inorganic devices. Energy Environ. Sci. 12(10), 2983–2990 (2019). https://doi.org/10.1039/c9ee01777a
  12. R.A. Kishore, A. Nozariasbmarz, B. Poudel, M. Sanghadasa, S. Priya, Ultra-high performance wearable thermoelectric coolers with less materials. Nat. Commun. 10, 1765 (2019). https://doi.org/10.1038/s41467-019-09707-8
  13. S. Hong, Y. Gu, J.K. Seo, J. Wang, P. Liu et al., Wearable thermoelectrics for personalized thermoregulation. Sci. Adv. 5(5), eaaw0536 (2019). https://doi.org/10.1126/sciadv.aaw0536
  14. A.R. Li, C.G. Fu, X.B. Zhao, T.J. Zhu, High-performance Mg3Sb2-xBix thermoelectrics: progress and perspective. Research 2020, 1934848 (2020). https://doi.org/10.34133/2020/1934848
  15. B.B. Jiang, Y. Yu, J. Cui, X.X. Liu, L. Xie et al., High-entropy-stabilized chalcogenides with high thermoelectric performance. Science 371(6531), 830–834 (2021). https://doi.org/10.1126/science.abe1292
  16. T.J. Abraham, D.R. MacFarlane, J.M. Pringle, Seebeck coefficients in ionic liquids -prospects for thermo-electrochemical cells. Chem. Commun. 47(22), 6260–6262 (2011). https://doi.org/10.1039/c1cc11501d
  17. Z. Liu, G. Chen, Advancing flexible thermoelectric devices with polymer composites. Adv. Mater. Technol. 5(7), 2000049 (2020). https://doi.org/10.1002/admt.202000049
  18. Y. Fan, Z. Liu, G. Chen, Recent progress in designing thermoelectric metal-organic frameworks. Small 17(38), 2100505 (2021). https://doi.org/10.1002/smll.202100505
  19. N. Kim, S. Lienemann, I. Petsagkourakis, D.A. Mengistie, S. Kee et al., Elastic conducting polymer composites in thermoelectric modules. Nat. Commun. 11, 1424 (2020). https://doi.org/10.1038/s41467-020-15135-w
  20. Y. Yang, H.J. Hu, Z.Y. Chen, Z.Y. Wang, L.M. Jiang et al., Stretchable nanolayered thermoelectric energy harvester on complex and dynamic surfaces. Nano Lett. 20(6), 4445–4453 (2020). https://doi.org/10.1021/acs.nanolett.0c01225
  21. Z. Liu, X. Wang, S. Wei, H. Lv, J. Zhou et al., A wavy-structured highly stretchable thermoelectric generator with stable energy output and self-rescuing capability. CCS Chem. 3(10), 2404–2414 (2021). https://doi.org/10.31635/ccschem.021.202101077
  22. H. Lv, L. Liang, Y. Zhang, L. Deng, Z. Chen et al., A flexible spring-shaped architecture with optimized thermal design for wearable thermoelectric energy harvesting. Nano Energy 88, 106260 (2021). https://doi.org/10.1016/j.nanoen.2021.106260
  23. T.J. Abraham, D.R. MacFarlane, J.M. Pringle, High Seebeck coefficient redox ionic liquid electrolytes for thermal energy harvesting. Energy Environ. Sci. 6(9), 2639–2645 (2013). https://doi.org/10.1039/c3ee41608a
  24. R. Hu, B.A. Cola, N. Haram, J.N. Barisci, S. Lee et al., Harvesting waste thermal energy using carbon-nanotube-based thermo-electrochemical cell. Nano Lett. 10(3), 838–846 (2010). https://doi.org/10.1021/nl903267n
  25. Y. Liu, H. Wang, P.C. Sherrell, L. Liu, Y. Wang et al., Potentially wearable thermo-electrochemical cells for body heat harvesting: from mechanism, materials, strategies to applications. Adv. Sci. 8(13), 2100669 (2021). https://doi.org/10.1002/advs.202100669
  26. T.I. Quickenden, C.F. Vernon, Thermogalvanic conversion of heat to electricity. Sol. Energy 36(1), 63–72 (1986). https://doi.org/10.1016/0038-092X(86)90061-7
  27. E.L. Yee, R.J. Cave, K.L. Guyer, P.D. Tyma, M.J. Weaver, A survey of ligand effects upon the reaction entropies of some transition metal redox couples. J. Am. Chem. Soc. 101(5), 1131–1137 (1979). https://doi.org/10.1021/ja00499a013
  28. B. Yu, J. Duan, H. Cong, W. Xie, R. Liu et al., Thermosensitive crystallization-boosted liquid thermocells for low-grade heat harvesting. Science 370(6514), 342–346 (2020). https://doi.org/10.1126/science.abd6749
  29. J. Duan, G. Feng, B. Yu, J. Li, M. Chen et al., Aqueous thermogalvanic cells with a high Seebeck coefficient for low-grade heat harvest. Nat. Commun. 9, 5146 (2018). https://doi.org/10.1038/s41467-018-07625-9
  30. M.S. Romano, N. Li, D. Antiohos, J.M. Razal, A. Nattestad et al., Carbon nanotube - reduced graphene oxide composites for thermal energy harvesting applications. Adv. Mater. 25(45), 6602–6606 (2013). https://doi.org/10.1002/adma.201303295
  31. B. Guo, Y. Hoshino, F. Gao, K. Hayashi, Y. Miura et al., Thermocells driven by phase transition of hydrogel nanops. J. Am. Chem. Soc. 142(41), 17318–17322 (2020). https://doi.org/10.1021/jacs.0c08600
  32. K. Kim, H. Lee, Thermoelectrochemical cells based on Li+/Li redox couples in LiFSI glyme electrolytes. Phys. Chem. Chem. Phys. 20(36), 23433–23440 (2018). https://doi.org/10.1039/c8cp03155j
  33. D.R. MacFarlane, M. Forsyth, P.C. Howlett, M. Kar, S. Passerini et al., Ionic liquids and their solid-state analogues as materials for energy generation and storage. Nat. Rev. Mater. 1, 15005 (2016). https://doi.org/10.1038/natrevmats.2015.5
  34. S. Pu, Y. Liao, K. Chen, J. Fu, S. Zhang et al., Thermogalvanic hydrogel for synchronous evaporative cooling and low-grade heat energy harvesting. Nano Lett. 20(5), 3791–3797 (2020). https://doi.org/10.1021/acs.nanolett.0c00800
  35. G. Wu, Y. Xue, L. Wang, X. Wang, G. Chen, Flexible gel-state thermoelectrochemical materials with excellent mechanical and thermoelectric performances based on incorporating Sn2+/Sn4+ electrolyte into polymer/carbon nanotube composites. J. Mater. Chem. A 6(8), 3376–3380 (2018). https://doi.org/10.1039/c7ta11146k
  36. P. Yang, K. Liu, Q. Chen, X. Mo, Y. Zhou et al., Wearable thermocells based on gel electrolytes for the utilization of body heat. Angew. Chem. Int. Ed. 55(39), 12050–12053 (2016). https://doi.org/10.1002/anie.201606314
  37. L. Jin, G.W. Greene, D.R. MacFarlane, J.M. Pringle, Redox-active quasi-solid-state electrolytes for thermal energy harvesting. ACS Energy Lett. 1(4), 654–658 (2016). https://doi.org/10.1021/acsenergylett.6b00305
  38. Y. Liu, S. Zhang, Y. Zhou, M.A. Buckingham, L. Aldous et al., Advanced wearable thermocells for body heat harvesting. Adv. Energy Mater. 10(48), 2002539 (2020). https://doi.org/10.1002/aenm.202002539
  39. Y. Zhou, Y. Liu, M.A. Buckingham, S. Zhang, L. Aldous et al., The significance of supporting electrolyte on poly (vinyl alcohol)–iron(II)/iron(III) solid-state electrolytes for wearable thermo-electrochemical cells. Electrochem. Commun. 124, 106938 (2021). https://doi.org/10.1016/j.elecom.2021.106938
  40. Z. Liu, Q. Yang, D. Wang, G. Liang, Y. Zhu et al., A flexible solid-state aqueous Zinc hybrid battery with flat and high-voltage discharge plateau. Adv. Energy Mater. 9(46), 1902473 (2019). https://doi.org/10.1002/aenm.201902473
  41. Z. Wang, H. Li, Z. Tang, Z. Liu, Z. Ruan et al., Hydrogel electrolytes for flexible aqueous energy storage devices. Adv. Funct. Mater. 28(48), 1804560 (2018). https://doi.org/10.1002/adfm.201804560
  42. C.G. Han, X. Qian, Q. Li, B. Deng, Y. Zhu et al., Giant thermopower of ionic gelatin near room temperature. Science 368(6495), 1091–1098 (2020). https://doi.org/10.1126/science.aaz5045
  43. Y. Huang, Z. Li, Z. Pei, Z. Liu, H. Li et al., Solid-state rechargeable Zn//NiCo and Zn-air batteries with ultralong lifetime and high capacity: the role of a sodium polyacrylate hydrogel electrolyte. Adv. Energy Mater. 8(31), 1802288 (2018). https://doi.org/10.1002/aenm.201802288
  44. M. Chen, J. Chen, W. Zhou, X. Han, Y. Yao et al., Realizing an all-round hydrogel electrolyte toward environmentally adaptive dendrite-free aqueous Zn-MnO2 batteries. Adv. Mater. 33(9), 2007559 (2021). https://doi.org/10.1002/adma.202007559
  45. J. Ma, J. Lee, S.S. Han, K.H. Oh, K.T. Nam et al., Highly stretchable and notch-insensitive hydrogel based on polyacrylamide and milk protein. ACS Appl. Mater. Interfaces 8(43), 29220–29226 (2016). https://doi.org/10.1021/acsami.6b10912
  46. J.P. Gong, Why are double network hydrogels so tough? Soft Matter 6(12), 2583–2590 (2010). https://doi.org/10.1039/b924290b
  47. R.S. Rivlin, A.G. Thomas, Rupture of rubber. I. Characteristic energy for tearing. J. Polym. Sci. 10(3), 291–318 (1953). https://doi.org/10.1002/pol.1953.120100303
  48. S.H. Shaikh, S.A. Kumar, Polyhydroxamic acid functionalized sorbent for effective removal of chromium from ground water and chromic acid cleaning bath. Chem. Eng. J. 326, 318–328 (2017). https://doi.org/10.1016/j.cej.2017.05.151
  49. R. Niu, Z.H. Qin, F. Ji, M. Xu, X.L. Tian et al., Hybrid pectin-Fe3+/polyacrylamide double network hydrogels with excellent strength, high stiffness, superior toughness and notch-insensitivity. Soft Matter 13(48), 9237–9245 (2017). https://doi.org/10.1039/c7sm02005h
  50. J.Y. Sun, X. Zhao, W.R.K. Illeperuma, O. Chaudhuri, K.H. Oh et al., Highly stretchable and tough hydrogels. Nature 489, 133–136 (2012). https://doi.org/10.1038/nature11409
  51. M.A. Buckingham, S. Hammoud, H. Li, C.J. Beale, J.T. Sengel et al., A fundamental study of the thermoelectrochemistry of ferricyanide/ferrocyanide: cation, concentration, ratio, and heterogeneous and homogeneous electrocatalysis effects in thermogalvanic cells. Sustain. Energy Fuels 4(7), 3388–3399 (2020). https://doi.org/10.1039/d0se00440e
  52. Y.V. Kuzminskii, V.A. Zasukha, G.Y. Kuzminskaya, Thermoelectric effects in electrochemical systems. Nonconventional thermogalvanic cells. J. Power Sources 52(2), 231–242 (1994). https://doi.org/10.1016/0378-7753(94)02015-9
  53. M. Rahimi, A.P. Straub, F. Zhang, X. Zhu, M. Elimelech et al., Emerging electrochemical and membrane-based systems to convert low-grade heat to electricity. Energy Environ. Sci. 11(2), 276–285 (2018). https://doi.org/10.1039/c7ee03026f
  54. T. Matsuda, T. Nakajima, Y. Fukuda, W. Hong, T. Sakai et al., Yielding criteria of double network hydrogels. Macromolecules 49(5), 1865–1872 (2016). https://doi.org/10.1021/acs.macromol.5b02592
  55. T. Sakai, Y. Akagi, S. Kond, U. Chung, Experimental verification of fracture mechanism for polymer gels with controlled network structure. Soft Matter 10(35), 6658–6665 (2014). https://doi.org/10.1039/c4sm00709c
  56. G.J. Lake, A.G. Thomas, The strength of highly elastic materials. Proc. R. Soc. Lond. Ser. A Math. Phys. Sci. 300, 108–119 (1967). https://doi.org/10.1098/rspa.1967.0160
  57. W. Lim, I. Lee, D. Sylvester, D. Blaauw, 8.2 batteryless sub-nW Cortex-M0+ processor with dynamic leakage-suppression logic. In: 2015 IEEE ISSCC Digest Technic. Pap. (2015). https://doi.org/10.1109/ISSCC.2015.7062968
  58. P.P. Mercier, S. Bandyopadhyay, A.C. Lysaght, K.M. Stankovic, A.P. Chandrakasan, A sub-nW 2.4 GHz transmitter for low data-rate sensing applications. IEEE J. Solid State Circ. 49(7), 1463–1474 (2014). https://doi.org/10.1109/JSSC.2014.2316237
  59. L. Liang, H. Lv, X.L. Shi, Z. Liu, G. Chen et al., A flexible quasi-solid-state thermoelectrochemical cell with high stretchability as an energy-autonomous strain sensor. Mater. Horiz. 8(10), 2750–2760 (2021)
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