N-type Thermoelectrics Research Articles

Synergistic effects of hybrid n-doping on the thermoelectric performance and air-stability of water-processable single-walled carbon nanotubes

Organic thermoelectrics (TEs) based on carbon nanotubes (CNTs) have attracted much attention with their inherent advantages, such as, earth-abundant elements, broad electronic tunability, and excellent mechanical compliance. However, the inferior TE performance and doping stability of n-type CNTs to those of p-type CNTs have been bottlenecks to establish CNT-based next-generation TEs. Herein, we report a hybrid n-doping method that improves the n-type TE performance and long-term air-stability of water-processable single-walled CNT (SWCNT) and carboxymethyl cellulose (CMC) composite. The hybrid n-doping process with polyethyleneimine (PEI) n-dopant contains primary addition and secondary immersion doping, which causes a simultaneous increase in electrical conductivity and Seebeck coefficient through efficient n-doping and surface energy filtering effect, respectively. Furthermore, the hybrid-doped films exhibit superior long-term stability by inhibiting the oxidation of SWCNT/CMC at nanoscale, which allows to ensure the initial power factor even after storing in ambient for a month. Finally, we successfully demonstrated hybrid-doped SWCNT/CMC-based TEGs with long-term stable output characteristics. This work can offer insights to develop efficient and air-stable n-type organic TE materials and devices.

Flexible and air-stable n-type oleylamine/carbon nanotube hybrid yarns for high-performance wearable thermoelectric generators

Wearable thermoelectric generators (TEGs), envisioned to harness the temperature gradient (ΔT) between the human body and the environment into electricity, hold great promise for powering wearable electronics. However, their practical application has been hampered by the scarcity of flexible n-type thermoelectric (TE) materials boasting both high performance and long-term air stability. Here, we introduce a significant advancement by developing an n-type TE material through immersing carbon nanotube yarn (CNTY) into an oleylamine (OAm)/ethanol solution, followed by drying under atmospheric conditions. The resulting OAm/CNTY exhibits a Seebeck coefficient of -80.48 μV K-1, an electrical conductivity of 1353.18 S cm-1 and a power factor of 876.25 μW m-1 K-2, all while exhibiting exceptional mechanical flexibility. Notably, this hybrid yarn maintains stable n-type behavior even after enduring exposure to air for over 370 days, surpassing previous n-type TE materials based on CNT fibers and CNTY. Leveraging this advancement, we construct a prototype wearable TEG by alternately embroidering pristine p-type CNTY and n-type OAm/CNTY into a polyester spacer fabric, electrically connecting them in series using conductive silver paint. The resulting wearable TEG, featuring with 150 p-n couples, yields an output voltage of 705.94 mV and a maximum output power of 44.34 μW at a ΔT of 40 K. This groundbreaking work opens new avenues for the development of high-performance, air-stable, and flexible n-type TE material, ushering in a new era for wearable TEGs.

Development of High Performance Thermoelectric Polymers via Doping or Dedoping Engineering.

It is of great significance to develop high-performance thermoelectric (TE) materials, because they can be used to harvest waste heat into electricity and there is abundant waste heat on earth. The conventional TE materials are inorganic semimetals or semiconductors like Bi2Te3 and its derivatives. However, they have problems of high cost, scarce/toxic elements, high thermal conductivity, and poor mechanical flexibility. Organic TE materials emerged as the next-generation TE materials because of their merits including solution processability, low cost, abundant element, low intrinsic thermal conductivity, and high mechanical flexibility. Organic TE materials are mainly conducting polymers because of their high conductivity. Both the conductivity and Seebeck coefficient depend on the doping level, and they are interdependent. Hence, the TE properties of polymers can be improved through doping/dedoping engineering. There are three types of doping forms, oxidative (or reductive) doping, protonic acid doping, and charge transfer doping. Accordingly, they can be dedoped by different approaches. In this article, we review the methods to dope and dedope p-type and n-type TE polymers and the combination of doping and dedoping to optimize their TE properties. Secondary doping is also covered, since it can significantly enhance the conductivity of some TE polymers.

Enhancing n-type PbTe thermoelectric performance through Cd alloying and strategic defects management

The significant performance disparity between n-type and p-type PbTe hinders their commercial viability in thermoelectric (TE) applications. While conventional multi-element alloying has demonstrably improved n-type PbTe thermoelectrics, it introduces stability concerns and cost escalation. Here, we propose a simpler approach utilizing a single isovalent element alloying strategy with Cd and defect management to enhance the TE performance of n-type PbTe. Cd doping widens the bandgap, leading to an increased effective mass and Seebeck coefficient, particularly at higher temperatures due to improved Cd solubility. However, as documented in previous studies on the PbTe-Cd system, Cd introduction can potentially deteriorate TE performance by reducing carrier mobility. To address this, we implemented defect engineering to optimize carrier mobility. A small excess of Pb atoms was introduced to occupy intrinsic Pb vacancies, achieving a remarkable 65.5 % enhancement in carrier mobility. Consequently, the maximum power factor of Cd-alloyed Pb1.01Te samples reaches 31.5 μW cm−1 K−2, marking a significant 69.3 % improvement compared to pristine PbTe. Additionally, the Cd-induced bandgap widening effectively mitigates bipolar diffusion. This, combined with enhanced phonon scattering due to the secondary CdTe phase, results in a 34.3 % decrease in thermal conductivity. By leveraging the multifaceted effects of Cd alloying and defect management, the ZT value of Pb1.01Te-2 %Cd samples reaches 1.35 at 782 K. These findings offer a new perspective on the versatile use of single isovalent element alloying strategy and performance optimization in other TE materials.

Tailoring interfacial states for improved n-type bismuth telluride thermoelectrics

Efforts to enhance the thermoelectric (TE) efficiency of n-type bismuth telluride (BTS) have focused on leveraging 2D nanostructures, as they have been proven effective in inhibiting phonon transport and simultaneously improving electrical properties. Herein, we introduce g-C3N4 as a suitable candidate for disrupting phonon transport, with the potential to finely tune charge carrier mobility. Crucially, our investigation provides insights into the potential of externally introduced conducting states as a feasible strategy for facilitating carrier transport at heterogeneous interfaces. In contrast, the carrier scattering and localization events play an inverse role. By carefully modulating the competition, we effectively increase carrier mobility, boosting electrical conductivity and optimizing the power factor. This orchestrated strategy leads to a high figure of merit (ZT) of 1.29 at 400 K and an average ZT (ZTave) of 1.20 within 300–500 K. At temperature difference ∆T = 180 K, a maximum power output Pmax = 0.91 W and a 6.2 % conversion efficiency (η) can be achieved over the fabricated TE module. Our findings underscore the potential of 2D nanomaterials and interfacial engineering (IE) as a promising avenue for unlocking the full potential of n-type thermoelectric materials, advancing sustainable and efficient TE power generation.

Universality of optoelectronic and thermoelectric properties of novel two-dimensional CrSiM2N (M=As, P and N[dbnd]Se, Te) monolayers and their vdWHs with MoTe2

In this study, we introduce a novel two-dimensional (2D) monolayer of CrSiM2N (M = As, P and NSe, Te) and explore its electronic properties. For the first time, we employ density functional theory and investigate the electronic and thermoelectric (TE) properties of CrSiM2N (M = As, P and NSe, Te) monolayers. Our calculated phonon band structure confirms that these monolayers are stable and can potentially be synthesized experimentally. The CrSiM2N (M = As, P and NSe, Te) monolayers exhibit an indirect band nature, with the CBM and VBM located at the K and G-points of the first Brillouin zone, respectively. We have also calculated the thermoelectric properties of these systems, which suggest that these monolayers could play a crucial role in enhancing the thermoelectric performance. Furthermore, we investigated the electronic, optical and thermoelectric properties of CrSiM2N (M = As, P and NSe, Te) and MoTe2 van der Waals heterostructures (vdWHs). The electronic band structure exhibits an indirect semiconductor nature, with the conduction band maxima and valence band minima originating from the CrSiM2N (M = As, P and NSe, Te) and MoTe2 monolayers, thereby confirming a type II band alignment. The optical properties indicate that these vdWHs can absorb a broad range of light, from the ultraviolet to the visible and infrared regions. We demonstrated that CrSiM2N (M = As, P and NSe, Te) monolayers exhibit p-type TE behavior, while their vdWHs counterparts exhibit n-type TE behavior.

Alcohol-Processable All-Polymer n-Type Thermoelectrics.

The general strategy for n-type organic thermoelectric is to blend n-type conjugated polymer hosts with small molecule dopants. In this work, all-polymer n-type thermoelectric is reported by dissolving a novel n-type conjugated polymer and a polymer dopant, poly(ethyleneimine) (PEI), in alcohol solution, followed by spin-coating to give polymer host/polymer dopant blend film. To this end, an alcohol-soluble n-type conjugated polymer is developed by attaching polar and branched oligo (ethylene glycol) (OEG) side chains to a cyano-substituted poly(thiophene-alt-co-thiazole) main chain. The main chain results in the n-type property and the OEG side chain leads to the solubility in hexafluorineisopropanol (HFIP). In the polymer host/polymer dopant blend film, the Coulombic interaction between the dopant counterions and the negatively charged polymer chains is reduced and the ordered stacking of the polymer host is preserved. As a result, the polymer host/polymer dopant blend exhibits the power factor of 36.9µWm-1K-1, which is one time higher than that of the control polymer host/small molecule dopant blend. Moreover, the polymer host/polymer dopant blend shows much better thermal stability than the control polymer host/small molecule dopant blend. This research demonstrates the high performance and excellent stability of all-polymer n-type thermoelectric.

Effect of graphene oxide and carbon black on the thermoelectric performance of niobium doped strontium titanate

Strontium titanate-based ceramics are promising n-type thermoelectrics due to their low cost and high thermal and chemical stability. Here, SrTi0.85Nb0.15O3 was prepared with carbon additions of electrochemically produced graphene oxide (eGO) and commercially available carbon black (CB). Ceramic samples were sintered at 1700 K under a reducing atmosphere. XRD, HR-TEM and Raman spectra confirmed the matrix phase was cubic perovskite; there were no carbon residues. By incorporating graphene oxide, the electrical conductivity increased nine-fold to 2818 S cm−1 at 300 K as a result of enhanced carrier mobility. In contrast, the carbon black samples exhibited low density and a small average grain size of ∼1 μm. High-resolution X-ray photoelectron spectroscopy revealed the presence of a large number of ionised impurities in the carbon black samples, which significantly enhanced scattering effects; low thermal conductivities of 1.7 W m−1 K−1 were achieved at 873 K. The work reveals that eGO promotes charge transport in SrTiO3, while CB significantly suppresses phonon transport. Both effects are relevant to the development of other thermoelectrics.

N-DMBI Doping of Carbon Nanotube Yarns for Achieving High n-Type Thermoelectric Power Factor and Figure of Merit.

The application of carbon nanotube (CNT) yarns as thermoelectric materials for harvesting energy from low-grade waste heat including that generated by the human body, is attracting considerable attention. However, the lack of efficient n-type CNT yarns hinders their practical implementation in thermoelectric devices. This study reports efficient n-doping of CNT yarns, employing 4-(1, 3-dimethyl-2, 3-dihydro-1H-benzimidazole-2-yl) phenyl) dimethylamine (N-DMBI) in alternative to conventional n-dopants, with o-dichlorobenzene emerging as the optimal solvent. The small molecular size of N-DMBI enables highly efficient doping within a remarkably short duration (10s) while ensuring prolonged stability in air and at high temperature (150°C). Furthermore, Joule annealing of the yarns significantly improves the n-doping efficiency. Consequently, thermoelectric power factors (PFs) of 2800, 2390, and 1534µWm-1K-2 are achieved at 200, 150, and 30°C, respectively. The intercalation of N-DMBI molecules significantly suppresses the thermal conductivity, resulting in the high figure of merit (ZT) of 1.69×10-2 at 100°C. Additionally, a π-type thermoelectric module is successfully demonstrated incorporating both p- and n-doped CNT yarns. This study offers an efficient doping strategy for achieving CNT yarns with high thermoelectric performance, contributing to the realization of lightweight and mechanically flexible CNT-based thermoelectric devices.

Electron-withdrawing quinone polymers with enhanced conjugated planarity for n-type organic thermoelectrics

A new electron-withdrawing quinone unit was developed for n-type thermoelectrics. Two n-type polymers were constructed, and the polymer with selenophene exhibited enhanced planarity and better thermoelectric performance.

Synergistic carrier and phonon transport advance Ag dynamically-doped n-type PbTe thermoelectrics via Mn alloying

Optimizing n-type PbTe thermoelectric materials to match their better-performing p-type counterparts is critical for realizing their practical applications.

High-Performance Paper-Based Thermoelectric Generator from Cu2SnS3 Nanocubes and Bulk-Traced Bismuth.

Flexible paper-based thermoelectric generators (PTEGs) have drawn significant interest in recent years due to their various advantages such as flexibility, adaptability, environment friendliness, low cost, and easy fabrication process. However, the reported PTEG's output performance still lags behind the performance of other flexible devices as it is not so easy to obtain a compact film on a paper-based substrate with desirable power output with the standard thermoelectric (TE) materials that have been previously utilized. In this direction, Cu2SnS3 (CTS), an earth-abundant, ternary sulfide, can be a good choice p-type semiconductor, when paired with a suitable n-type TE material. In this article, CTS nanocubes are synthesized via a simple hot injection method and a thick film device on emery paper was prepared and optimized. Furthermore, a flexible, 20-pair PTEG is fabricated with p-type CTS legs and traced and pressed n-type bismuth legs assembled using Kapton tape that produced a significantly high output power of 2.18 μW (output power density ∼0.85 nW cm-2 K-1) for a temperature gradient of ΔT = 80 K. The TE properties are also supported by finite element simulation. The bending test conducted for the PTEG suggests device stability for up to 800 cycles with <0.05% change in the internal resistance. A proof-of-concept field-based demonstration for energy harvesting from waste heat of a motorbike exhaust is shown recovering an output power of ∼42 nW for ΔT = 20 K, corroborating the experimental and theoretical results.

Optimized Thermoelectric Cooler Performance by the Structure-Matching Design of Asymmetrical p/n-Type Legs.

Commercial Bi2Te3-based thermoelectric (TE) coolers typically comprise equal-size p- and n-type legs. However, this traditional structure limits the cooling temperature differences of TE coolers (TECs) due to identical current density, when their electrical or thermal characteristics differ significantly. This work presents a novel design of p- and n-type TE legs to optimize the performance of TECs. The cooling properties of the materials are initially calculated by theoretical equations and then evaluated by using a combination of finite element simulations and experiments. The research findings suggest that by utilizing higher ZT p-type materials to enhance the TEC cooling performance, further optimization of the ratio of the cross-sectional area of the TE legs (Ap/An) improves the structural matching of the legs, which achieves the maximum figure of merit Z and leads to a 5.4% increase in cooling power density. Additionally, the TEC with optimized Ap/An increases the cooling temperature difference by 3.3 and 2.7 K for the same current at hot side temperatures of 300 and 315 K, respectively, while the coefficient of performance remains unchanged. Moreover, the maximum cooling temperature difference reaches 70 and 74 K, respectively. We anticipate that our results will guide the design and optimization of the TECs.

Enhanced Thermoelectric Performance in the SrTi0.85Nb0.15O3 Oxide Nanocomposite with Fe2O3-Functionalized Graphene.

Doped SrTiO3 is considered one of the potential thermoelectric (TE) candidates but its TE figure of merit, ZT needs to be improved for practical application of electricity generation from high-grade waste-heat. In the present work, enhanced TE performance has been realized for SrTi0.85Nb0.15O3 (STN) perovskite adopting the strategy of composite formation with Fe2O3-functionalized graphene (FGR). We have achieved a maximum electrical conductivity of 1.4 × 105 S m-1 for 1 wt % FGR added to STN, which is around 1185% larger than that of pristine STN. The presence of FGR in the STN matrix acts as a mobility booster of electrons, overcoming the effect of Anderson localization of electrons, which impedes the electron transport in STN. This is evident from the order of magnitude increase in weighted mobility of STN after FGR addition. Furthermore, the incorporation of FGR causes about a 34% decrease in the lattice thermal conductivity. The Debye-Callaway model demonstrates that the phonon-phonon Umklapp scattering is primarily responsible for reduced thermal conductivity. The presence of FGR sheets along the grain boundaries of STN, Fe2O3 nanoparticles, and lattice imperfections gives rise to the glass-like temperature-independent phonon mean-free-path, especially above Debye temperature. The maximum ZT ∼ 0.57 has been obtained at 947 K for the 1 wt % FGR sample, which is around 420% higher than that of pristine STN. Furthermore, we have fabricated a prototype of a four-legged n-type TE module, demonstrating one of the highest power outputs of 18 mW among reported oxide thermoelectrics.

Effective Thermoelectric Switch of Hollow Weakly-Coupled Molecular Junction Based on Twist Angle Effect with Boron-Doping

ABSTRACT Rational design and adjustment of flexible thermoelectric devices are key points for sustainable and effective thermoelectric conversion, which remains a fundamental challenge due to inherent high thermal conductivity and uncontrolled carrier concentration induced by non-uniform dispersion. Under ingenious combination of weakly-coupled hollow interface and nanotube structure, thermoelectric performance of a dumbbell-like molecular junction comprised of a phenyl-terminated polyyne as central molecule and two semi-infinite 1D single-walled carbon nanotube (SWCNT) as electrodes has been investigated at certain twisted angles (θ). The results indicate that molecule twisting can be reviewed as an effective thermoelectric switch to coordinatingly control electronic and phononic transmission properties simultaneously. Resonance of molecular discrete state and electrode continuous state leads to low thermal conductance, which is sensitively affected by twist angle. Meanwhile, cyclic transformation between p-type and n-type flexible thermoelectrics can be realized by manipulating twist angle in a certain period of rotation. Thermoelectric performance of such a molecular junction can be further improved by boron atom doping at head-to-tail positions, and an excellent figure of merit (ZT = 1.75) is observed near Fermi level under 25° twisted angle. This result inspires an effective strategy to modulate and control thermoelectric conversion, which will greatly broaden applications in thermoelectric twistronics.

High-performance Sb2Si2Te6 thermoelectric device

High-performance thermoelectric (TE) devices are promising for waste-heat recovery and power generation. Recently, Sb2Si2Te6 has been demonstrated as a promising p-type TE material with high performance and low cost. However, Sb2Si2Te6-based TE devices have not yet been fabricated. The performance of TE devices depends on not only TE materials, but also electrode materials and inner interfaces. Herein, we utilize the high throughput strategy to screen the appropriate electrode material and find that cobalt exhibits a low contact resistance (2.47 μΩ cm−2) and a high shear strength (18.03 MPa). Furthermore, we successfully fabricate one eight-couple Sb2Si1.99Ge0.01Te6 (p-type)/Yb0.3Co4Sb12 (n-type) TE module with optimized geometric parameters by the finite element method. The module exhibits a high output power density (0.92 W cm−2) and a decent energy conversion efficiency (4.2%) under a temperature difference of 500 K. Our studies will promote further development of Sb2Si2Te6 materials and Sb2Si2Te6-based devices.

An overview of oxidation in hybrid and glass-based protective coatings for thermoelectric materials for medium-temperature range applications

ABSTRACT Several oxidation protective coatings, both glass-based and ceramic/polymer hybrid coatings, for p- and n-type thermoelectrics were designed at the Politecnico di Torino in recent years, and they were characterised and tested under relevant conditions. The ‘glass-ceramic route’ to obtain a thermo-mechanical compatible and high-temperature resistant coated thermoelectric is discussed with some examples. Oxidation tests demonstrated the effectiveness of the coatings for the protection of both n- and p-type thermoelectrics.

Neutron-irradiated effect on the thermoelectric properties of Bi2Te3-based thermoelectric leg

Thermoelectric (TE) materials working in radioisotope thermoelectric generators are irradiated by neutrons throughout its service; thus, investigating the neutron irradiation stability of TE devices is necessary. Herein, the influence of neutron irradiation with fluences of 4.56 × 1010 and 1 × 1013 n/cm2 by pulsed neutron reactor on the electrical and thermal transport properties of n-type Bi2Te2.7Se0.3 and p-type Bi0.5Sb1.5Te3 thermoelectric alloys prepared by cold-pressing and molding is investigated. After neutron irradiation, the properties of thermoelectric materials fluctuate, which is related to the material type and irradiation fluence. Different from p-type thermoelectric materials, neutron irradiation has a positive effect on n-type Bi2Te2.7Se0.3 materials. This result might be due to the increase of carrier mobility and the optimization of electrical conductivity. Afterward, the effects of p-type and n-type TE devices with different treatments on the output performance of TE devices are further discussed. The positive and negative effects caused by irradiation can cancel each other to a certain extent. For TE devices paired with p-type Bi0.5Sb1.5Te3 and n-type Bi2Te2.7Se0.3 thermoelectric legs, the generated power and conversion efficiency are stable after neutron irradiation.

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N-type All-Polymer Conductors and High-ZT Thermoelectrics.

N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest of 78 S-1 , power factor (PF) of 163 μW m-1 K-2 , and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to , and atypical decreased thermal conductivity ( ) with increased doping ratio contribute to the promising performance.

Solution-processed flexible n-type S-doped Ag2Se thermoelectric generators for near-ambient-temperature energy harvest†

Among the different technologies to harvest renewable energy, thermoelectric (TE) generators (TEGs) represent a highly promising route capable of converting heat to electricity based on the Seebeck effect. Here, a new room temperature (RT) one-pot solution synthesis approach was proposed, together with a sulfur-doping strategy, to optimize the flexibility and the power factor of n-type S-doped Ag2Se TE thin films deposited by solution-processes, requiring only mild post-deposition annealing at 150 °C. Optimized S-doped flexible Ag2Se thin films exhibited a maximum power factor of ∼2058 μW/m/K2 at RT, allowing for the fabrication of flexible TEGs with a maximum power output (Pmax) of 3.98 μW under a near-RT ΔT of 31 K, equivalent to a power density of 11.06 W/m2. Multidomain applications were further demonstrated by these heavy-metal–free, flexible TEGs to harvest near-RT waste heat from laptop computers, non-concentrated sun light, and human body together with the realization of a self-powered motion detector. The current findings open promising paths for innovations on low-cost wearable smart electronics and energy harvesting.