High-performance Thermoelectric Materials Research Articles

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, scare/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.

GaInX3(X = S; Se; Te): ultra-low thermal conductivity and excellent thermoelectric performance

Abstract Seeking intrinsically low thermal conductivity materials is a viable strategy in the pursuit of high-performance thermoelectric materials. Here, by using first-principles calculations and semiclassical Boltzmann transport theory, we systemically investigate the carrier transport and thermoelectric properties of monolayer Janus GaInX3 (X = S; Se; Te). It is found that the lattice thermal conductivities can reach values as low as 3.07 Wm−1K−1, 1.16 Wm−1K−1 and 0.57 Wm−1K−1 for GaInS3, GaInSe3, and GaInTe3, respectively, at room temperature. These notably low thermal conductivity is attributed to strong acoustic-optical phonon coupling caused by the presence of low-frequency optical phonons in GaInX3 materials. Furthermore, by integrating the characteristics of electronic and thermal transport, the dimensionless figure of merit ZT can reach maximum values of 0.95, 2.37, and 3.00 for GaInS3, GaInSe3, and GaInTe3, respectively. Our results suggest monolayer Janus GaInX3 (X = S; Se; Te) are promising candidates for thermoelectric and heat management applications.

3D-Printed Soft Temperature Sensors Based on Thermoelectric Effects for Fast Mapping of Localized Temperature Distributions.

We propose a novel design of thermoelectric (TE) effect-based soft temperature sensors for directly monitoring localized subtle temperature stimuli. This design integrates rheology-engineered three-dimensional (3D) printing of high-performance carbon-based TE materials and polymer-based viscoelastic materials with low thermal conductivity. Rheological engineering of carbon nanotube (CNT) TE inks ensures the 3D printing of highly sensitive TE sensing units on directly written 3D soft platforms. Additionally, we pre-dope CNT inks with p- and n-type organic dopants to achieve high sensitivity and a fast response to temperature changes. The introduced 3D soft platforms with low thermal conductivity lead to an efficient thermal gradient on TE sensing units in the out-of-plane direction. Furthermore, encapsulating the temperature sensor array with the same polymer-based materials as the 3D soft platforms facilitates independent detection of localized temperature stimuli by minimizing thermal interaction between sensing units, resulting in precise temperature mapping by localized detection. Our 3D-printed soft temperature sensors exhibit high sensitivity to relatively small temperature changes, with a minimum sensing resolution of 0.1 K within tens of milliseconds. Moreover, the temperature sensor array not only detects localized temperature stimuli by imaging the temperature distribution but also demonstrates remarkable mechanical reliability against repetitive deformation with high accuracy.

Enhanced thermoelectric figure of merit in graphene nanoribbons by creating a distortion and transition-metal doping

Thermoelectric (TE) materials have the exceptional ability to directly convert waste heat into electricity and theoretical studies-based guidance is an effective way to investigate high-performance nanostructured TE materials throughout a range of temperatures. Herein, we studied the influence of distortion and transition metal (TM) atoms (V, Cr, Co and Pt) on the electronic and TE properties of armchair graphene nanoribbons (AGNRs) at various temperatures. The results showed that TM-doping and distortion might significantly alter the electronic structure of AGNRs. The band gap and valence band convergence are reduced as a result of the synergistic effect. A higher TE figure of merit results from a combination of decreased heat conductivity and increased electrical conductivity brought about by the electronic structural change. This study proposes that by doping and distortion-induced TE characteristics engineering of AGNR, high-performance nanostructured TE materials may be produced that have a wide range of TE applications.

Dual-Cation CuAgSe-Based Material: Rapid Mass Transfer in Synthesis and High Thermoelectric Performance Realization.

Understanding mass transfer mechanisms is vital for developing new material synthesis and densification technologies. Ion transport, serving both mass and charge transfer, is essential for the rapid preparation of high-performance fast ionic conductor thermoelectric materials like Zn4Sb3 and Cu2Q (Q = S, Se). In the case of dual-cation fast ion conductor materials like CuAgSe, exploring the relationship between cation transport becomes pertinent. In this study, copper (Cu) and selenium (Se) undergo a reaction in the presence of an electric field (∼15 A), resulting in the formation of the CuSe compound. Subsequent to this initial reaction, a subsequent thermal environment facilitates the interaction among Cu, CuSe, and Ag2Se, culminating in the rapid formation and densification of CuAgSe (with a relative density exceeding 99%) in just 30 s. Evidently, the diffusion of copper ions substantiates a pivotal role in facilitating mass transfer. As a result, CuAg1+xSe samples with different silver contents (x = 0.01, 0.02, 0.03, 0.04 and 0.05) can effectively inhibit cation vacancy, and introduce highly ordered Ag nanotwins to enhance the electrical transport performance. For CuAg1.04Se, a peak ZT value of 1.0 can be achieved at 673 K, which is comparable to the literatures. This work will guide the future electric field-assisted rapid mass transfer of materials.

Anomalous thermal transport and high thermoelectric performance of Cu-based vanadate CuVO3

Thermoelectric (TE) conversion technology, capable of transforming heat into electricity, is critical for sustainable energy solutions. Many promising TE materials contain rare or toxic elements, so the development of cost-effective and eco-friendly high-performance TE materials is highly urgent. Herein, we explore the thermal transport and TE properties of transition metal vanadate CuVO3 by using first-principles calculation. On the basis of the unified theory of heat conduction, we uncover the hierarchical thermal transport feature in CuVO3, where wave-like tunneling makes a significant contribution to the lattice thermal conductivity (κl) and results in the anomalously weak temperature dependence of κl. This is primarily attributable to the complex phononic band structure caused by the heterogeneity of Cu–O and V–O bonds. Simultaneously, we report a high power factor of 5.45 mW·K−2·m−1 realized in hole-doped CuVO3, which arises from a high electrical conductivity and a large Seebeck coefficient enabled by the multiple valleys and large electronic density of states near the valence band edge. Impressively, the low κl and the high power factor make p-typed CuVO3 have ZT of up to 1.39, with the excellent average ZT above 1.0 from 300 to 600 K, which is superior to most reported Cu-based TE materials. Our findings suggest that the CuVO3 compound is a promising candidate for energy conversion applications in innovative TE devices.

Realizing BiCuSeO-based thermoelectric device for ultrahigh carrier mobility through texturation

The thermoelectric conversion technology, as a promising renewable energy technology, enables direct and efficient conversion between electricity and heat. In the past ten years, there has been an increasing curiosity towards oxide thermoelectric materials due to their environmentally friendly nature, low cost, and excellent thermal and chemical stability. However, the intrinsic low carrier mobility of BiCuSeO limits its potential to be a high-performance thermoelectric material. Herein, we propose a dynamic sintering approach to enhance carrier mobility of BiCuSeO. As a result, carrier mobility at room temperature of three-step textured Bi0.94Pb0.06Cu0.97Se1.05O0.95 reaches an ultrahigh value of 13.1 cm2 V−1 s−1, which is the highest reported in the conventional doping of BiCuSeO system. Based on the ultrahigh carrier mobility, the power factor of three-step textured Bi0.94Pb0.06Cu0.97Se1.05O0.95 sample could reached 20 μV cm−1 K−2 near room temperature, and the average power factor of 300–923 K could reach 18.0 μV cm−1 K−2, effectively optimizing the electrical performance throughout the entire test temperature span. As a result, we successfully attain a ZT of ∼ 1.5 at 923 K and a ZTave of 0.89 within the temperature span of 300–923 K for three-step textured Bi0.94Pb0.06Cu0.97Se1.05O0.95 sample. Based on the outstanding performance, we have successfully built a 7-pair thermoelectric device based on three-step textured Bi0.94Pb0.06Cu0.97Se1.05O0.95 paired with the N-type two-step textured Bi2Te2.7Se0.3Cu0.01, which is the first BiCuSeO-based thermoelectric device. The thermoelectric device, exhibits a maximum conversion efficiency of 2.8 % at the temperature difference 215 K and simultaneously achieves a cooling temperature difference of 23.5 K with the hot end at 286 K. This work indicates that texturation is an effective approach for enhancing the carrier mobility of oxide TE materials. Besides, BiCuSeO oxyselenide is promising for pollution-free and cost-effective thermoelectric devices of power generation and cooling, thereby offering potential implications for sustainable energy solutions.

High-throughput thermoelectric materials screening by deep convolutional neural network with fused orbital field matrix and composition descriptors

Thermoelectric materials harvest waste heat and convert it into reusable electricity. Thermoelectrics are also widely used in inverse ways such as refrigerators and cooling electronics. However, most popular and known thermoelectric materials to date were proposed and found by intuition, mostly through experiments. Unfortunately, it is extremely time and resource consuming to synthesize and measure the thermoelectric properties through trial-and-error experiments. Here, we develop a convolutional neural network (CNN) classification model that utilizes the fused orbital field matrix and composition descriptors to screen a large pool of materials to discover new thermoelectric candidates with power factor higher than 10 μW/cm K2. The model used our own data generated by high-throughput density functional theory calculations coupled with ab initio scattering and transport package to obtain electronic transport properties without assuming constant relaxation time of electrons, which ensures more reliable electronic transport properties calculations than previous studies. The classification model was also compared to some traditional machine learning algorithms such as gradient boosting and random forest. We deployed the classification model on 3465 cubic dynamically stable structures with non-zero bandgap screened from Open Quantum Materials Database. We identified many high-performance thermoelectric materials with ZT > 1 or close to 1 across a wide temperature range from 300 to 700 K and for both n- and p-type doping with different doping concentrations. Moreover, our feature importance and maximal information coefficient analysis demonstrates two previously unreported material descriptors, namely, mean melting temperature and low average deviation of electronegativity, that are strongly correlated with power factor and thus provide a new route for quickly screening potential thermoelectrics with high success rate. Our deep CNN model with fused orbital field matrix and composition descriptors is very promising for screening high power factor thermoelectrics from large-scale hypothetical structures.

Synergistically optimized electron and phonon transport in high-performance copper sulfides thermoelectric materials via one-pot modulation

Optimizing thermoelectric conversion efficiency requires the compromise of electrical and thermal properties of materials, which are hard to simultaneously improve due to the strong coupling of carrier and phonon transport. Herein, a one-pot approach realizing simultaneous second phase and Cu vacancies modulation is proposed, which is effective in synergistically optimizing thermoelectric performance in copper sulfides. Multiple lattice defects, including nanoprecipitates, dislocations, and nanopores are produced by adding a refined ratio of Sn and Se. Phonon transport is significantly suppressed by multiple mechanisms. An ultralow lattice thermal conductivity is therefore obtained. Furthermore, extra Se is added in the copper sulfide for optimizing electrical transport properties by inducing generating Cu vacancies. Ultimately, an excellent figure of merit of ~1.6 at 873 K is realized in the Cu1.992SSe0.016(Cu2SnSe4)0.004 bulk sample. The simple strategy of inducing compositional and structural modulation for improving thermoelectric parameters promotes low-cost high-performance copper sulfides as alternatives in thermoelectric applications.

Multinary Tetrahedrite (Cu12-x-yMxNySb4S13) Nanoparticles: Tailoring Thermal and Optical Properties with Copper-Site Dopants.

Tetrahedrite (Cu12Sb4S13) is an earth-abundant and nontoxic compound with prospective applications in green energy technologies such as thermoelectric waste heat recycling or photovoltaic power generation. A facile, one-pot solution-phase modified polyol method has been developed that produces high-purity nanoscale tetrahedrite products with exceptional stoichiometric and phase control. This modified polyol method is used here to produce phase-pure quaternary and quintenary tetrahedrite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, or Co. This is the first time that Cu-site codoped quintenary tetrahedrite and Mn-doped quaternary tetrahedrite have been produced by a solution-phase method. X-ray diffraction shows phase-pure tetrahedrite, while scanning and transmission electron microscopy show the size and morphology of the nanomaterials. Energy dispersive X-ray spectroscopy confirms nanoparticles have near-stoichiometric elemental compositions. Thermal stability of quintenary codoped tetrahedrite material is analyzed using thermogravimetric analysis, finding that codoping with Mn, Fe, Ni, and Zn increased thermal stability while codoping with cobalt decreased thermal stability. This is the first systematic study of the optical properties of quaternary and quintenary tetrahedrite nanoparticles doped on the Cu-site. Visible-NIR diffuse reflectance spectroscopy reveals that the quaternary and quintenary tetrahedrite nanoparticles have direct optical band gaps ranging from 1.88 to 2.04 eV. Data from thermal and optical characterization support that codoped tetrahedrite nanoparticles are composed of quintenary grains. This research seeks to enhance understanding of the material properties of tetrahedrite, leading to the optimization of sustainable, nontoxic, and high-performance photovoltaic and thermoelectric materials.

Enhanced thermoelectric properties of Mg2Si0.3Sn0.7 via Bi-doping under high pressure

A series of n-type Mg2(Si0.3Sn0.7)1-xBix compounds with 0≤x≤0.02 were successfully synthesized through a combined approach involving solid-state reaction, high-pressure synthesis, and spark plasma sintering techniques. The method yielded homogeneously distributed single-phase materials at the micron scale, although minor compositional variations were detected within nanoscale precipitates embedded in the grains. The sample with Bi content of 0.01 exhibited enhanced thermoelectric properties, reaching a peak thermoelectric figure of merit (ZT) of 1.45 at 700 K while maintaining an average ZT of about 1.1 over the temperature range of 300−773 K. The enhancement in thermoelectric performance is ascribed to the optimized carrier concentration, band convergence, and refined microstructure. The findings suggest a simplified approach to doping that could be beneficial in creating high-performance thermoelectric materials for energy conversion.

Recent Developments on Flexible Materials for Thermoelectrics

In recent decades, thermoelectric materials have gained a significant attention due to their ability to directly convert waste heat into electricity. While extensive research has been focused on enhancing the thermoelectric properties of inorganic bulk materials, a new frontier has emerged in this area as flexible thermoelectric materials. These flexible thermoelectrics are driven by the limitations posed by the rigidity, less functional and toxicity of conventional inorganic thermoelectric materials. Despite notable achievements in the development of high-performance flexible thermoelectric materials, they still pose inferior figure of merit (zT) in comparison to their inorganic counterparts. This review encompasses various aspects of flexible thermoelectric materials including theoretical foundations which highlight the principles that explain the concepts and parameters of thermoelectricity to enhance the overall performance, serving as a foundation for understanding the subsequent developments. Further it is overviewed in detail the corresponding state of the art in development of conducting thermoelectric polymers, inorganic-polymer composites, carbon-based thermoelectric and inorganic thermoelectrics on flexible substrates to enhance their thermoelectric performances. Finally it includes the overlook to the future of flexible thermoelectric for wearable thermoelectrics.

Boosting Thermoelectric Performance of PbBi2 Te4 via Reduced Carrier Scattering and Intensified Phonon Scattering.

Materials with low intrinsic lattice thermal conductivity are crucial in the pursuit of high-performance thermoelectric (TE) materials. Here, the TE properties of PbBi2 Te4-x Sex (0 ≤ x ≤ 0.6) samples are systematically investigated for the first time. Doping with Se in PbBi2 Te4 can simultaneously reduce carrier concentration and increase carrier mobility. The Seebeck coefficient is significantly increased by doping with Se, based on the density functional theory calculation, it is shown to be due to the increased bandgap and electronic density of states. In addition, the lattice strain is enhanced due to the difference in the size of Se and Te atoms, and the multidimensional defects formed by Se doping, such as vacancies, dislocations, and grain boundaries, enhance the phonon scattering and reduce the lattice thermal conductivity by about 37%. Finally, by using Se doping to reduce carrier concentration and thermal conductivity, a large ZTmax = 0.56 (at 574K) is achieved for PbBi2 Te3.5 Se0.5 , which is around 64% larger than those of the PbBi2 Te4 pristine sample. This work not only demonstrates that PbBi2 Te4 is a potential medium temperature thermoelectric material, but also provides a reference for enhancing thermoelectric properties through defect and energy band engineering.

Ag, Pb co-doped SnSe high performance thermoelectric materials

SnSe, as a novel thermoelectric material, has ultrahigh thermoelectric properties in its single crystals, while the thermoelectric properties of polycrystals need to be further improved. Introducing atomic disorder to increase the lattice anharmonicity of the material is a typical strategy to reduce the lattice thermal conductivity and enhance the thermoelectric properties. Ag and Pb co-doping increased the effective carrier mass of the samples, and the resultant strong phonon scattering leads to a drastic decrease of the lattice thermal conductivity over the whole temperature range, and at the same time, optimizes the energy-band structure of SnSe, which finally significantly increases the Seebeck coefficient of SnSe. However, the electrical properties of SnSe deteriorate due to Pb elemental doping, so we introduce Ag atoms with higher intrinsic conductivity to increase its conductivity. At 800 K, the electrical conductivity of the Sn0.82Ag0.08Pb0.1Se sample is about twice as much as that of the undoped SnSe, and the thermal conductivity is 0.28 W mK−1. The ZT value of Sn0.82Ag0.08Pb0.1Se sample peaked at ∼1.33 at 800 K compared to only ∼0.48 for undoped SnSe. The ZT ave value of Sn0.82Ag0.08Pb0.1Se sample in the temperature range of 300–500 K was ∼0.36 compared to only ∼0.083 for undoped SnSe samples.

Developing High-Performance and Low-Cost Paint Thermoelectric Materials for Low-Midtemperature Applications.

Most thermoelectric (TE) materials used to convert heat energy into electrical energy are expensive and, to a certain degree, toxic. Moreover, due to the chemical complexity in the synthesis process, some of the TE materials are not reproducible. Similarly, the scarcity of TE materials hampers their scalability. To address the above issues, this study presents an inexpensive, nontoxic, scalable, and highly reproducible paint-based TE module for the conversion of heat energy to electrical energy. Transport properties with structural analysis indicate that the electrical conductivity of the paint TE material is controlled by the concentration of graphite and sodium silicate, while the Seebeck coefficient is dominated by the ratio of n- and p-type Bi-Sb-Te. The results indicate that the as-developed TE module can withstand an operating temperature of up to 160 °C. At a temperature of 57 °C, the highest power factors of the as-synthesized n- and p-type TE paints are 1.34 and 1.42 μW/(cm K2), respectively. It is also found that the TE module can have a higher output voltage when the cold side of the TE module is allowed to float in the air in comparison to that when it is in contact with the human body. The performance of the paint-based TE module is measured on five parts of the body, namely, the chest, palm, leg, wrist, and neck; the wrist has the highest open-circuit voltage of 1.9 mV, indicating its suitability for wearable applications. Finally, at a temperature gradient of 30 °C, a maximum output power of 6.8 μW is attained.

Stability, thermodynamic, electronic, and thermoelectric properties of triclinic Cu[formula omitted]Se structure

The conversion of heat into electricity using the thermoelectric effect is a crucial issue to tackle the ever-increasing global energy consumption. Cu2Se is one of the high-performance thermoelectric materials due to its liquid-like atomic structure, which minimizes the phonon-derived thermal conductivity. Nevertheless, the unambiguous atomic structure of the low-temperature phase, α-Cu2Se, remains controversial. By employing a combination of theoretical approaches including an evolutionary algorithm for structural searching, density functional theory, and lattice dynamics, the α-Cu2Se phase is proposed to crystalize in the dynamically stable triclinic Cu2Se structure (s.g. P1) which can be regarded as a monoclinic polymorph (s.g. P21/c†) through slight distortion. The corresponding heat capacity (CV) and Debye temperature (ΘD) are 0.37 J/g K and 276 K, respectively, indicating low thermal conductivity in the material. The semiconducting P1 phase possesses an indirect gap of 1.0 eV. Additionally, based on the Boltzmann transportation theory, fundamental thermoelectric parameters around the transition temperature (300–500 K) are investigated. Beyond the semiconducting phase, a novel metallic phase identified as the triclinic P1̄ phase is also discovered, exhibiting a two-dimensional (2D) crystal geometry.

High thermoelectric performance near the Mott–Ioffe–Regel limit in CuxS0.6Te0.4 meta-phases

The meta-phase, characterized by crystal-amorphicity duality in the extremely special case, has garnered considerable interests due to its glass-like thermal conductivity and tunable conduction mechanisms for carriers. However, the impact of crystal-amorphicity duality on the electrical and thermal transports remains elusive, and the carrier concentration in the meta-phase is rarely tuned in a wide range for optimized thermoelectric properties. Herein, through a combination of molecular dynamic simulations, chemical bonding analysis, and structural characterization, we reveal the glass-like distribution of Cu cations modulated by the mismatched S/Te anions in CuxS0.6Te0.4 meta-phase. Such unique atomic structure leads to hopping conduction of carriers and extremely low thermal conductivity. The carrier concentration is effectively optimized by tuning the Cu content in CuxS0.6Te0.4. Finally, we achieve a high zT of 1.4 at 900 K for Cu2.01S0.6Te0.4 sample, which is three times larger than those of Cu2S and Cu2Te matrixes. Remarkably, the high zT value is attained near the Mott–Ioffe–Regel Limit where the carrier mean free path is close to the average atomic distance. Our findings shed light on a new route to discovering high-performance thermoelectric materials.

Suppressed lattice thermal conductivity in porous compounds for high-performance thermoelectric applications

Traditional zinc blende semiconductor materials of groups II–VI and III–V exhibit excellent electrical properties, yet suffer from oversized lattice thermal conductivity, causing poor thermoelectric performance. Herein, we have explored an alternative metastable phase of those materials, namely, porous phase. Compared with the stable zinc blende structure, which has simple crystal structure with nearly isotropic bonding feature, porous compounds exhibit complex bonding hierarchy and softened acoustic phonon modes with strong anharmonicity, reducing the lattice thermal conductivity by nearly two orders of magnitude. As an outstanding representative of porous compound family, the suppressed thermal conductivity [∼0.76 W/(m K) at room temperature] combined with enhanced Seebeck coefficient makes porous MgTe a high-performance thermoelectric material with figure of merit above unity at n-type doping and high temperature. This work highlights the important role of intrinsic porosity in design of high-performance thermoelectric materials with low lattice thermal conductivity.

Phonon transport properties of Janus Pb2 XAs (X = P, Sb, and Bi) monolayers: A DFT study

Grasping the underlying mechanisms behind the low lattice thermal conductivity of materials is essential for the efficient design and development of high-performance thermoelectric materials and thermal barrier coating materials. In this paper, we present a first-principles calculations of the phonon transport properties of Janus Pb2PAs and Pb2SbAs monolayers. Both materials possess low lattice thermal conductivity, at least two orders of magnitude lower than graphene and h-BN. The room temperature thermal conductivity of Pb2SbAs (0.91 W/mK) is only a quarter of that of Pb2PAs (3.88 W/mK). We analyze in depth the bonding, lattice dynamics, and phonon mode level information of these materials. Ultimately, it is determined that the synergistic effect of low group velocity due to weak bonding and strong phonon anharmonicity is the fundamental cause of the intrinsic low thermal conductivity in these Janus structures. Relative regular residual analysis further indicates that the four-phonon processes are limited in Pb2PAs and Pb2SbAs, and the three-phonon scattering is sufficient to describe their anharmonicity. In this study, the thermal transport properties of Janus Pb2PAs and Pb2SbAs monolayers are illuminated based on fundamental physical mechanisms, and the low lattice thermal conductivity endows them with the potential applications in the field of thermal barriers and thermoelectrics.

A novel solution-based approach for PANI growth on PEDOT:PSS film to fabricate PEDOT:PSS/PANI-H2SO4 bilayer and its application in thermoelectric energy harvesting

The construction of bilayer or multilayer structures has been recognized as one of the most promising strategies for exploring high-performance organic thermoelectric materials. In this study, a novel poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate)/polyaniline (PEDOT:PSS/PANI) bilayer film was successfully fabricated through a facile solution method, wherein PANI was initially dissolved in concentrated sulfuric acid (H2SO4) to form a homogenous solution which was then applied to the PEDOT:PSS film. Benefiting from the introduction of PANI, the Seebeck coefficient of the PEDOT:PSS film was improved from 16.34 to 23.17 μV K−1, while the electrical conductivity experienced a remarkable enhancement, reaching 723.34 S cm−1. Accordingly, the resulting PEDOT:PSS/PANI-H2SO4 bilayer film demonstrated a high power factor (PF) of 38.83 μW m−1 K−2, which further increased to 44.38 μW m−1 K−2 at 380 K. Hence, this technique offers a facile method to fabricate large-scale PEDOT:PSS/PANI-H2SO4 bilayer films, expanding application fields of PANI via solution-based preparation.