An Emerging Liquid-Crystalline Conducting Polymer Thermoelectrics: Opportunities and Challenges

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An Emerging Liquid-Crystalline Conducting Polymer Thermoelectrics: Opportunities and Challenges
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An Emerging Liquid-Crystalline Conducting Polymer Thermoelectrics: Opportunities and Challenges - Nano-Micro Letters

Thermoelectric (TE) materials, being capable of converting waste heat into electricity, are pivotal for sustainable energy solutions. Among emerging TE materials, organic TE materials, particularly conjugated polymers, are gaining prominence due to their unique combination of mechanical flexibility, environmental compatibility, and solution-processable fabrication. A notable candidate in this field is poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), a liquid-crystalline conjugated polymer, with high charge carrier mobility and adaptability to melt-processing techniques. Recent advancements have propelled PBTTT’s figure of merit from below 0.1 to a remarkable 1.28 at 368 K, showcasing its potential for practical applications. This review systematically examines strategies to enhance PBTTT’s TE performance through doping (solution, vapor, and anion exchange doping), composite engineering, and aggregation state controlling. Recent key breakthroughs include ion exchange doping for stable charge modulation, multi-heterojunction architectures reducing thermal conductivity, and proton-coupled electron transfer doping for precise Fermi-level tuning. Despite great progress, challenges still persist in enhancing TE conversion efficiency, balancing or decoupling electrical conductivity, Seebeck coefficient and thermal conductivity, and leveraging melt-processing scalability of PBTTT. By bridging fundamental insights with applied research, this work provides a roadmap for advancing PBTTT-based TE materials toward efficient energy harvesting and wearable electronics.

As wearable electronics and IoT sensors proliferate, the demand for flexible, melt-processable thermoelectric (TE) materials that convert body heat into electricity is soaring. Now, researchers from Shenzhen University, led by Prof. Guangming Chen, comprehensively review the latest leaps in poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT)—a liquid-crystalline conjugated polymer whose figure of merit has catapulted from <0.1 to a record 1.28 at 368 K through asymmetric doping, multi-heterojunction architectures and phonon-blocking strategies.

Why PBTTT Matters

  • Highest Organic ZT: 1.28 rivals inorganic Bi2Te3 yet retains mechanical flexibility and solution/melt processability.
  • Scalable Processing: Compatible with roll-to-roll blade coating, floating-film transfer and high-T rubbing; 35 × 21 cm2 uniform films demonstrated.
  • Melt Advantage: 140–180 °C smectic phase enables solvent-free alignment, cutting fabrication cost and environmental impact.

Innovative Design & Features

  • Multi-Heterojunction Architecture: Alternating PBTTT/PDPPSe-12 nanolayers suppress out-of-plane κ to 0.06 W m-1 K-1 (55 % reduction) while preserving σ = 196 S cm-1, yielding an exceptional power factor of 628 μW m-1 K-2.
  • PCET & NEII Doping: Proton-coupled electron-transfer tunes Fermi level within ±25 meV precision; nanoconfined electrochemical ion implantation achieves 100 nm spatial resolution for independent crystalline/amorphous domain control.
  • Anion-Exchange Doping: Ionic-liquid mediators push conductivity to 1,120 S cm-1 without disrupting π–π stacking, maintaining high Seebeck coefficient.

Applications & Outlook

  • Flexible TEGs: 522 nW output under 38 K gradient, 95 % retention after 100,000 bending cycles; 3.3 mV on human skin.
  • Energy Filtering: Low-energy carrier filtering and tie-chain blending decouple σ–S trade-off, opening routes to >2 mW m-1 K-2 power factors.
  • Next Steps: Integration with melt-spinning fibers and jointless p–n legs for watt-level wearable modules; AI-guided side-chain design to push ZT > 2.

This review bridges fundamental insights and scalable manufacturing, positioning PBTTT as a front-runner for eco-friendly, mass-produced organic thermoelectrics. Stay tuned for more advances from Prof. Chen’s group!

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Electrochemistry
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry
Thermoelectrics
Physical Sciences > Materials Science > Materials for Energy and Catalysis > Thermoelectrics
Liquid Crystals
Physical Sciences > Materials Science > Soft Materials > Liquid Crystals
Polymers
Physical Sciences > Materials Science > Soft Materials > Polymers
Nanoscale Design, Synthesis and Processing
Physical Sciences > Materials Science > Nanotechnology > Nanoscale Design, Synthesis and Processing
  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.