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Title: Unconventional Thermoelectric Materials for Energy Harvesting and Sensing Applications

Journal Article · · Chemical Reviews

Heat is an abundant but often wasted source of energy. Thus, harvesting just a portion of this tremendous amount of energy holds significant promise for a more sustainable society. While traditional solid-state inorganic semiconductors have dominated the research stage on thermal-to-electrical energy conversion, carbon-based semiconductors have recently attracted a great deal of attention as potential thermoelectric materials for low-temperature energy harvesting, primarily driven by the high abundance of their atomic elements, ease of processing/manufacturing, and intrinsically low thermal conductivity. This quest for new materials has resulted in the discovery of several new kinds of thermoelectric materials and concepts capable of converting a heat flux into an electrical current by means of various types of particles transporting the electric charge: (i) electrons, (ii) ions, and (iii) redox molecules. This has contributed to expanding the applications envisaged for thermoelectric materials far beyond simple conversion of heat into electricity. This is the motivation behind this review. This work is divided in three sections. In the first section, we present the basic principle of the thermoelectric effects when the particles transporting the electric charge are electrons, ions, and redox molecules and describe the conceptual differences between the three thermodiffusion phenomena. In the second section, we review the efforts made on developing devices exploiting these three effects and give a thorough understanding of what limits their performance. In the third section, we review the state-of-the-art thermoelectric materials investigated so far and provide a comprehensive understanding of what limits charge and energy transport in each of these classes of materials.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
Alice Wallenberg Foundation; Linkoping University; Marie Sklodowska-Curie Foundation; Olle Engkvists Stiftelse; Swedish Research Council; USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1821642
Report Number(s):
NREL/JA--5K00-79566; MainId:35787; UUID:43e60368-408d-4223-a7c1-56b835220c58; MainAdminID:62891
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Journal Issue: 20 Vol. 121; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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  • Dettlaff-Weglikowska, Urszula; Skákalová, Viera; Graupner, Ralf
  • Journal of the American Chemical Society, Vol. 127, Issue 14, p. 5125-5131 https://doi.org/10.1021/ja046685a
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Light-Weight Flexible Carbon Nanotube Based Organic Composites with Large Thermoelectric Power Factors journal September 2011
High-Yield Dispersions of Large-Diameter Semiconducting Single-Walled Carbon Nanotubes with Tunable Narrow Chirality Distributions journal February 2013
Ligand Coupling Symmetry Correlates with Thermopower Enhancement in Small-Molecule/Nanocrystal Hybrid Materials journal September 2014
Transparent Conductive Single-Walled Carbon Nanotube Networks with Precisely Tunable Ratios of Semiconducting and Metallic Nanotubes journal May 2008
Multicomponent Solubility Parameters for Single-Walled Carbon Nanotube−Solvent Mixtures journal August 2009
Improved Thermoelectric Behavior of Nanotube-Filled Polymer Composites with Poly(3,4-ethylenedioxythiophene) Poly(styrenesulfonate) journal December 2009
Electronic structure of atomically resolved carbon nanotubes journal January 1998
Helical microtubules of graphitic carbon journal November 1991
Two-dimensional charge transport in self-organized, high-mobility conjugated polymers journal October 1999
Highly anisotropic P3HT films with enhanced thermoelectric performance via organic small molecule epitaxy journal July 2016
Organic thermoelectric materials for energy harvesting and temperature control journal August 2016
Preparation and characterization of graphene oxide paper journal July 2007
DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes journal July 2009
Atomically precise bottom-up fabrication of graphene nanoribbons journal July 2010
High-efficiency electrochemical thermal energy harvester using carbon nanotube aerogel sheet electrodes journal February 2016
Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatography journal May 2011
Ionic thermoelectric gating organic transistors journal January 2017
High-performance and compact-designed flexible thermoelectric modules enabled by a reticulate carbon nanotube architecture journal March 2017
Flexible and self-powered temperature–pressure dual-parameter sensors using microstructure-frame-supported organic thermoelectric materials journal September 2015
Tailored semiconducting carbon nanotube networks with enhanced thermoelectric properties journal April 2016
Diameter-selective encapsulation of metallocenes in single-walled carbon nanotubes journal May 2005
Complex thermoelectric materials journal February 2008
An inconvenient truth about thermoelectrics journal February 2009
Stretchable active-matrix organic light-emitting diode display using printable elastic conductors journal May 2009
Optimization of the thermoelectric figure of merit in the conducting polymer poly(3,4-ethylenedioxythiophene) journal May 2011
High-performance flat-panel solar thermoelectric generators with high thermal concentration journal May 2011
Thermal conductivity of isotopically modified graphene journal January 2012
Engineered doping of organic semiconductors for enhanced thermoelectric efficiency journal May 2013
A general relationship between disorder, aggregation and charge transport in conjugated polymers journal August 2013
Semi-metallic polymers journal December 2013
Molecular design and control of fullerene-based bi-thermoelectric materials journal December 2015
Charge-transport model for conducting polymers journal November 2016
Modulation of thermal and thermoelectric transport in individual carbon nanotubes by fullerene encapsulation journal July 2017
Sorting carbon nanotubes by electronic structure using density differentiation journal October 2006
Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers journal September 2007
High-yield production of graphene by liquid-phase exfoliation of graphite journal August 2008
Polyethylene nanofibres with very high thermal conductivities journal March 2010
Advanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugation journal May 2010
High thermal conductivity of chain-oriented amorphous polythiophene journal March 2014
Exceptional thermoelectric properties of flexible organic−inorganic hybrids with monodispersed and periodic nanophase journal September 2018
Aqueous thermogalvanic cells with a high Seebeck coefficient for low-grade heat harvest journal December 2018
Polymer gels with tunable ionic Seebeck coefficient for ultra-sensitive printed thermopiles journal March 2019
Direct spinning and densification method for high-performance carbon nanotube fibers journal July 2019
Stretchable fabric generates electric power from woven thermoelectric fibers journal January 2020
Elastic conducting polymer composites in thermoelectric modules journal March 2020
A thermally activated and highly miscible dopant for n-type organic thermoelectrics journal July 2020
N-type organic thermoelectrics: demonstration of ZT > 0.3 journal November 2020
A high-conductivity n-type polymeric ink for printed electronics journal April 2021
Thermoelectric properties and performance of flexible reduced graphene oxide films up to 3,000 K journal February 2018
Flexible layer-structured Bi2Te3 thermoelectric on a carbon nanotube scaffold journal November 2018
Cellulose ionic conductors with high differential thermal voltage for low-grade heat harvesting journal March 2019
PEDOT:PSS/graphene quantum dots films with enhanced thermoelectric properties via strong interfacial interaction and phase separation journal April 2018
Giant power factors in p- and n-type large-area graphene films on a flexible plastic substrate journal November 2019
Iodine doped carbon nanotube cables exceeding specific electrical conductivity of metals journal September 2011
Systematic Conversion of Single Walled Carbon Nanotubes into n-type Thermoelectric Materials by Molecular Dopants journal November 2013
Development of n-type cobaltocene-encapsulated carbon nanotubes with remarkable thermoelectric property journal January 2015
Doping of single-walled carbon nanotube bundles by Brønsted acids journal January 2003
π-Conjugated molecules with fused rings for organic field-effect transistors: design, synthesis and applications journal January 2010
Enhancement of the thermoelectric properties in nanoscale and nanostructured materials journal January 2011
Flexible carbon nanotube papers with improved thermoelectric properties journal January 2012
Investigation of the kinetic and mass transport limitations in thermoelectrochemical cells with different electrode materials journal January 2014
The synergic regulation of conductivity and Seebeck coefficient in pure polyaniline by chemically changing the ordered degree of molecular chains journal January 2014
Abnormally enhanced thermoelectric transport properties of SWNT/PANI hybrid films by the strengthened PANI molecular ordering journal January 2014
Morphology and thermoelectric properties of graphene nanosheets enwrapped with polypyrrole journal January 2014
Preparation of polypyrrole/graphene nanosheets composites with enhanced thermoelectric properties journal January 2014
An efficient thermoelectric material: preparation of reduced graphene oxide/polyaniline hybrid composites by cryogenic grinding journal January 2015
Graphene boosts thermoelectric performance of a Zintl phase compound journal January 2015
Transparent and flexible organic semiconductor nanofilms with enhanced thermoelectric efficiency journal January 2014
Enhanced thermoelectric performance of PEDOT with different counter-ions optimized by chemical reduction journal January 2014
PANI/graphene nanocomposite films with high thermoelectric properties by enhanced molecular ordering journal January 2015
Enhanced thermoelectric property by the construction of a nanocomposite 3D interconnected architecture consisting of graphene nanolayers sandwiched by polypyrrole nanowires journal January 2015
Enhanced thermoelectric performance of PEDOT:PSS/PANI–CSA polymer multilayer structures journal January 2016
Temperature dependence of the electrode potential of a cobalt-based redox couple in ionic liquid electrolytes for thermal energy harvesting journal January 2016
Improving thermo-electrochemical cell performance by constructing Ag–MgO–CNTs nanocomposite electrodes journal January 2015
A review on mechanical exfoliation for the scalable production of graphene journal January 2015
Effective doping by spin-coating and enhanced thermoelectric power factors in SWCNT/P3HT hybrid films journal January 2015
Spray-printed CNT/P3HT organic thermoelectric films and power generators journal January 2015
Large in-plane/out-of-plane anisotropic conduction in PEDOT-based hybrid films: lamellar assemblies structured by mono-layered nanosheets journal January 2015
Acido-basic control of the thermoelectric properties of poly(3,4-ethylenedioxythiophene)tosylate (PEDOT-Tos) thin films journal January 2015
A review of carrier thermoelectric-transport theory in organic semiconductors journal January 2016
Ionic thermoelectric supercapacitors journal January 2016
Skutterudite with graphene-modified grain-boundary complexion enhances zT enabling high-efficiency thermoelectric device journal January 2017
Identification of a positive-Seebeck-coefficient exohedral fullerene journal January 2016
Engineering carrier scattering at the interfaces in polyaniline based nanocomposites for high thermoelectric performances journal January 2017
Enhanced power factor in flexible reduced graphene oxide/nanowires hybrid films for thermoelectrics journal January 2016
Thermoelectric power of oriented thin-film organic conductors journal January 2016
Improving the thermoelectric power factor of CNT/PEDOT:PSS nanocomposite films by ethylene glycol treatment journal January 2016
Flexible low-grade energy utilization devices based on high-performance thermoelectric polyaniline/tellurium nanorod hybrid films journal January 2016
Oxygen-induced doping on reduced PEDOT journal January 2017
Thermo-electrochemical cells for waste heat harvesting – progress and perspectives journal January 2017
The role of ion–water interactions in determining the Soret coefficient of LiCl aqueous solutions journal January 2017
High-performance thermoelectric materials based on ternary TiO 2 /CNT/PANI composites journal January 2018
Large n- and p-type thermoelectric power factors from doped semiconducting single-walled carbon nanotube thin films journal January 2017
Flexible unipolar thermoelectric devices based on patterned poly[K x (Ni-ethylenetetrathiolate)] thin films journal January 2017
Towards monochiral carbon nanotubes: a review of progress in the sorting of single-walled carbon nanotubes journal January 2018
Large-scalable RTCVD Graphene/PEDOT:PSS hybrid conductive film for application in transparent and flexible thermoelectric nanogenerators journal January 2017
Influence of crystallinity on the thermoelectric power factor of P3HT vapour-doped with F4TCNQ journal January 2018
A p-type multi-wall carbon nanotube/Te nanorod composite with enhanced thermoelectric performance journal January 2018
Ionic thermoelectric paper journal January 2017
Poly(3,4-ethylenedioxythiophene)-tosylate (PEDOT-Tos) electrodes in thermogalvanic cells journal January 2017
Solution-processable flexible thermoelectric composite films based on conductive polymer/SnSe 0.8 S 0.2 nanosheets/carbon nanotubes for wearable electronic applications journal January 2018
Thermoelectric properties of dispersant-free semiconducting single-walled carbon nanotubes sorted by a flavin extraction method journal January 2019
Farming thermoelectric paper journal January 2019
High thermoelectric power-factor composites based on flexible three-dimensional graphene and polyaniline journal January 2019
Flexible PANI/SWCNT thermoelectric films with ultrahigh electrical conductivity journal January 2018
The thermoelectrochemistry of the aqueous iron( ii )/iron( iii ) redox couple: significance of the anion and pH in thermogalvanic thermal-to-electrical energy conversion journal January 2018
Tailoring the framework of organic small molecule semiconductors towards high-performance thermoelectric composites via conglutinated carbon nanotube webs journal January 2018
N -Alkyl substituted 1 H -benzimidazoles as improved n-type dopants for a naphthalene-diimide based copolymer journal January 2018
High-performance n-type thermoelectric composites of acridones with tethered tertiary amines and carbon nanotubes journal January 2018
Small molecular hole-transporting materials (HTMs) in organic light-emitting diodes (OLEDs): structural diversity and classification journal January 2018
Chloride transport in conductive polymer films for an n-type thermoelectric platform journal January 2020
Carbon nanotube fibers with enhanced longitudinal carrier mobility for high-performance all-carbon thermoelectric generators journal January 2019
PEDOT thermoelectric composites with excellent power factors prepared by 3-phase interfacial electropolymerization and carbon nanotube chemical doping journal January 2019
Balancing the electrical conductivity and Seebeck coefficient by controlled interfacial doping towards high performance benzothienobenzothiophene-based organic thermoelectric materials journal January 2019
Carbon nanotube yarn based thermoelectric textiles for harvesting thermal energy and powering electronics journal January 2020
Hole-transporting materials for organic light-emitting diodes: an overview journal January 2019
Expression of interfacial Seebeck coefficient through grain boundary engineering with multi-layer graphene nanoplatelets journal January 2020
A high-performance and flexible thermoelectric generator based on the solution-processed composites of reduced graphene oxide nanosheets and bismuth telluride nanoplates journal January 2020
Salt doping to improve thermoelectric power factor of organic nanocomposite thin films journal January 2020
Influence of dopant size and doping method on the structure and thermoelectric properties of PBTTT films doped with F 6 TCNNQ and F 4 TCNQ journal January 2020
Bulk nanostructured thermoelectric materials: current research and future prospects journal January 2009
High performance organic semiconductors for field-effect transistors journal January 2010
Seebeck coefficients in ionic liquids –prospects for thermo-electrochemical cells journal January 2011
Methods for carbon nanotubes synthesis—review journal January 2011
Thermoelectric properties of nanocomposite thin films prepared with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) and graphene journal January 2012
Thermopower enhancement in conducting polymer nanocomposites via carrier energy scattering at the organic–inorganic semiconductor interface journal January 2012
Towards polymer-based organic thermoelectric generators journal January 2012
Thermoelectric composites of poly(3-hexylthiophene) and carbon nanotubes with a large power factor journal January 2013
Thermocharge of a hot spot in an electrolyte solution journal January 2013
Synthesis of electrically conducting organic polymers: halogen derivatives of polyacetylene, (CH) x journal January 1977
Flexible PEDOT electrodes with large thermoelectric power factors to generate electricity by the touch of fingertips journal January 2013
High Seebeck coefficient redox ionic liquid electrolytes for thermal energy harvesting journal January 2013
Metal-free oxygen reduction electrodes based on thin PEDOT films with high electrocatalytic activity journal January 2014
Specific salt effects on thermophoresis of charged colloids journal January 2014
Improved power factor of polyaniline nanocomposites with exfoliated graphene nanoplatelets (GNPs) journal January 2013
A wearable thermoelectric generator fabricated on a glass fabric journal January 2014
Large thermoelectric power factor in polyaniline/graphene nanocomposite films prepared by solution-assistant dispersing method journal January 2014
Polyanilines: a novel class of conducting polymers journal January 1989
Flexible thermoelectric generator for human body heat energy harvesting journal August 2012
A theoretical study on thermoelectric properties of graphene nanoribbons journal June 2009
Thermophoresis: The mass transfer mechanism in modified chemical vapor deposition journal September 1979
Fabrication of iodine-doped pentacene thin films for organic thermoelectric devices journal January 2011
Electrical transport in doped polyacetylene journal July 1980
Electrical and thermoelectric properties of single-wall carbon nanotube doped Bi2Te3 journal July 2012
Dependence on cation size of thermally induced capacitive effect of a nanoporous carbon journal August 2012
Effects of work function on thermal sensitivity of electrode potential journal June 2015
Thermoelectric energy recovery at ionic-liquid/electrode interface journal June 2015
Isotropic Seebeck coefficient of aligned single-wall carbon nanotube films journal December 2018
Enhanced thermoelectric properties of semiconducting carbon nanotube films by UV/ozone treatment journal October 2019
One-directional thermal transport in densely aligned single-wall carbon nanotube films journal November 2019
Sensitive and fast measurement of surface temperature with a thermogalvanic cell journal March 2020
Bulk electronic transport impacts on electron transfer at conducting polymer electrode–electrolyte interfaces journal November 2018
The best thermoelectric. journal July 1996
Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films journal August 2018
Thermoelectric properties of sorted semiconducting single-walled carbon nanotube sheets journal March 2019
A Review on the Performance of Organic Rankine Cycle with Different Heat Sources and Absorption Chillers journal March 2018
Suitability of a thermoelectric power generator for implantable medical electronic devices journal August 2007
Materials for thermoelectric energy conversion journal April 1988
Thermal non-equilibrium transport in colloids journal November 2010
Electronic properties of graphene: a perspective from scanning tunneling microscopy and magnetotransport journal April 2012
Thermoelectric properties of graphene nanoribbons, junctions and superlattices journal August 2010
Thermoelectric effects in graphene nanostructures journal March 2015
Synthesis and spectroscopic characterization of solution processable highly ordered polythiophene–carbon nanotube nanohybrid structures journal December 2009
Effects of ion concentration on thermally-chargeable double-layer supercapacitors journal October 2013
Dispenser-printed planar thick-film thermoelectric energy generators journal September 2011
Macroscopically aligned carbon nanotubes for flexible and high-temperature electronics, optoelectronics, and thermoelectrics journal December 2019
Flexible n-type thermoelectric composite films with enhanced performance through interface engineering and post-treatment journal May 2018
Polyvinyl alcohol covalently grafted CNT for free-standing, flexible, and high-performance thermoelectric generator film journal February 2019
Heat conduction in graphene: experimental study and theoretical interpretation journal September 2009
Flexible thermoelectric films with high power factor made of non-oxidized graphene flakes journal July 2019
Dependence of thermoelectric power and electrical conductivity on structural order of PEDOT-Tos-graphene nanocomposite via charge carrier mobility journal September 2019
Inkjet-printed flexible organic thin-film thermoelectric devices based on p- and n-type poly(metal 1,1,2,2-ethenetetrathiolate)s/polymer composites through ball-milling
  • Jiao, Fei; Di, Chong-an; Sun, Yimeng
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2013 https://doi.org/10.1098/rsta.2013.0008
journal April 2014
Non-Wiedemann-Franz behavior of the thermal conductivity of organic semiconductors journal February 2020
Soliton excitations in polyacetylene journal August 1980
Transport properties of alkali-metal-doped single-wall carbon nanotubes journal August 1998
Impurity scattering and Mott’s formula in graphene journal November 2007
Theory of enhancement of thermoelectric properties of materials with nanoinclusions journal June 2008
Enhanced thermoelectric figure of merit in edge-disordered zigzag graphene nanoribbons journal March 2010
Diameter dependence of thermoelectric power of semiconducting carbon nanotubes journal October 2015
Transport in Charged Colloids Driven by Thermoelectricity journal September 2008
Thermoelectric and Magnetothermoelectric Transport Measurements of Graphene journal March 2009
Anomalous Thermoelectric Transport of Dirac Particles in Graphene journal April 2009
Electrical Conductivity in Doped Polyacetylene journal October 1977
Energy Band-Gap Engineering of Graphene Nanoribbons journal May 2007
Thermopower of ionic conductors and ionic capacitors journal November 2020
New thermoelectric components using microsystem technologies journal June 2004
Wireless Sensor System for Industrial Applications Powered by Thermoelectric Generator
  • Boegel, Gerd vom; Meyer, Frederic; Kemmerling, Martin
  • 2014 European Conference on Smart Objects, Systems and Technologies (Smart SysTech), Smart SysTech 2014; European Conference on Smart Objects, Systems and Technologies https://doi.org/10.1109/SmartSysTech.2014.7156017
conference July 2014
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High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys journal May 2008
Two-Dimensional Phonon Transport in Supported Graphene journal April 2010
Strong, Light, Multifunctional Fibers of Carbon Nanotubes with Ultrahigh Conductivity journal January 2013
Advances in thermoelectric materials research: Looking back and moving forward journal September 2017
Giant thermopower of ionic gelatin near room temperature journal April 2020
Mixed Ionic-Electronic Transport in Polymers journal July 2021
Thermoelectric Properties of Semiconducting Polymers journal July 2020
Power Conversion Efficiency, Electrode Separation, and Overpotential in the Ferricyanide/Ferrocyanide Thermogalvanic Cell journal August 1996
The Power Conversion Efficiencies of a Thermogalvanic Cell Operated in Three Different Orientations journal November 1995
A Review of Power Generation in Aqueous Thermogalvanic Cells journal January 1995
Discharge Behavior of Redox Thermogalvanic Cells journal February 1976
Review—Micro and Nano-Engineering Enabled New Generation of Thermoelectric Generator Devices and Applications journal January 2017
Ionic Liquid Electrolytes for Thermal Energy Harvesting Using a Cobalt Redox Couple journal January 2014
Nitrogen- and Boron-Doped Carbon Nanotube Electrodes in a Thermo-Electrochemical Cell journal January 2012
Nitrogen Doping in Carbon Nanotubes journal September 2005
Synthesis and Characterization of Vertically Aligned Carbon Nanotube Forest for Solid State Fiber Spinning journal July 2012
Nano-Carbon Electrodes for Thermal Energy Harvesting journal January 2015
Thermoelectric Conversion by Thin-Layer Thermogalvanic Cells with Soluble Redox Couples journal April 1987
In-plane Thermal Conductivity Measurement of Conjugated Polymer Films by Membrane-based AC Calorimetry journal July 2016
Thermodynamics of Thermoelectric Phenomena and Applications journal August 2011
Recent Progress on PEDOT-Based Thermoelectric Materials journal February 2015
Thermocells for Hybrid Photovoltaic/Thermal Systems journal April 2020
Thermoelectric properties of sorted semiconducting single-walled carbon nanotube sheets dataset January 2021
Development of carbon nanotube organic thermoelectric materials using cyclodextrin polymer: control of semiconductor characteristics by the solvent effect journal January 2020
Giant Seebeck coefficient in semiconducting single-wall carbon nanotube film journal January 2014
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Improvement of thermoelectric performance of single-wall carbon nanotubes by heavy doping: Effect of one-dimensional band multiplicity journal November 2016