High Thermoelectric Efficiency Research Articles

Pressure-induced band gap enhancement and temperature-dependent thermoelectric characterization of semiconducting Transition Metal Chalcogenides LiMS (M = Cu, Ag)

The first principles study of Transition Metal Chalcogenides LiMS (M = Cu, Ag) has been conducted utilizing the concepts of Density Functional Theory (DFT). Both the compounds possess a cubic structure with space group F-43m. The mechanical stability of LiCuS and LiAgS has been predicted based on the values of elastic tensor. These Chalcogenides possess an interesting electronic band structure which reveals their semiconducting nature with a direct band gap. The electronic structure is further subjected to high pressure and the changes in band gap are deeply observed. For these materials, the changes in band gap in response to applied pressure suggest the possibility of their use in band gap engineering. The phonon curves are investigated over the Brillouin zone's high symmetry directions which reveal the lattice dynamical stability of the presently studied compounds. Moreover, the atoms present at different positions inside a crystal lattice exhibit vibrations of different intensities and in different directions which have been studied through the Eigenvector representations. The thermoelectric properties of LiCuS and LiAgS have been characterized using Boltzmann's theory over the range of temperature between 100 K and 1600 K. The calculated thermoelectric parameters reveal the high thermoelectric efficiency of these materials with excellent values of the figure of merit. The interesting properties of ternary Chalcogenides LiMS (M = Cu, Ag) make them promising candidates for thermoelectric applications.

The development and impact of tin selenide on thermoelectrics.

Thermoelectric technology experienced rapid development over the past 20 years, with the most promising applications being in both power generation and active cooling. Among existing thermoelectrics, tin selenide (SnSe) has had particularly rapid development owing to the unexpectedly high thermoelectric efficiency that has been continuously established over the past decade. Several transport mechanisms and strategies used to interpret and improve the thermoelectric performance of SnSe have been important for understanding and developing other material systems with SnSe-like characteristics. Similar to other thermoelectrics, building commercially viable SnSe-based devices requires advances in device efficiency and service stability. Further optimization across all material systems should enable thermoelectric technology to play a critical role in the future global energy landscape.

BAs/BlueP van der Waals heterostructures for photovoltaic and thermoelectric applications

The advancement of novel energy materials, encompassing photovoltaic and thermoelectric materials, assumes paramount significance in ameliorating the energy crisis and proactively combating climate change. The BAs/BlueP van der Waals heterostructure (vdWH), characterized by its outstanding optical absorption properties, high power conversion efficiency (PCE), and excellent thermoelectric performance, offers novel insights into the advancement of materials for photonic and thermoelectric applications. We have engineered a vdWH by combining BAs and BlueP, and conducted a comprehensive investigation of its electronic, optical, and thermoelectric properties. The BAs/BlueP vdWH demonstrates excellent thermodynamic and kinetic stability with type I band alignment, facilitating rapid interlayer electron-hole recombination. The remarkable optical absorption capability within the visible and ultraviolet (UV) spectral regions, coupled with an outstanding power conversion efficiency reaching up to 22.35 % under strain, firmly establishes the potential for utilization in photovoltaic conversion applications. At 1000 K, the significant ZT value (1.25) and high thermoelectric conversion efficiency (19.45 %) provide the theoretical foundation for its application in the field of thermoelectrics.

High power density charging-free thermally regenerative electrochemical flow cycle for low-temperature thermoelectric conversion

Low-temperature thermal energy widely exists in nature and is sustainable. The thermally regenerative electrochemical cycle (TREC) based on the Seebeck effect has attracted widespread attention due to its high thermoelectric efficiency and good cycle stability. However, it has a low power density and cannot sustain continuous operation for extended periods. This work proposes a continuous charging-free thermally regenerative electrochemically cycled flow battery (TREC-FB) system, which can discharge continuously at both high and low temperatures without the assistance of external power source. By adding guanidine hydrochloride (GdmCl) and inorganic salt ions (Cs+, Ca2+, Mg2+, etc.) to the K3Fe(CN)6/K4Fe(CN)6 and I2/KI electrolytes respectively, precipitates are formed in the electrolytes at low temperature and dissolve at high temperature, which creates the concentration gradient of ions. As a result, the temperature coefficient of the full cell increases from −2.24 mV/K to −3.6 mV/K, and both voltage and power density are doubled. Theoretical analysis of the temperature coefficient enhancement is conducted based on the Nernst equation, and the mechanism of the temperature coefficient enhancement is verified using UV–vis spectra. The discharging capacity and energy of the charging-free TREC-FB with high temperature coefficient reach 5 Ah/L and 1.9 kJ/L, respectively, and the thermoelectric efficiency reaches 8.9 % under sufficient heat recuperation. Two TREC-FBs at high and low temperatures are connected to carry out continuous operation experiments of the charging-free TREC-FB system. The use of charge-reinforced ion-selective membrane can effectively inhibit the migration of I− and I3− ions, achieving about 36 h of continuous operation, and the average power density achieves 0.6 W/m2.

Stability of phase composition and properties of Zn4+xSb3 medium-temperature thermoelectric material

The phase composition and thermoelectric properties of a β-Zn4Sb3 based material before and after thermocycling tests at 273–723 K have been studied. Specimens with stoichiometric Zn and Sb molar ratios and with additions of different excess Zn quantities have been synthesized by direct component smelting followed by spark plasma sintering. The phase composition and structure of the materials have been studied using X-ray diffraction and transmission electron microscopy. The thermal conductivity and specific heat of the materials have been measured with laser flash and differential scanning calorimetry techniques. The phase composition of the as-synthesized, as-sintered and as-thermocycled Zn4+xSb3 thermoelectric material has been found to vary depending on excess Zn content in the charge. Excess Zn has been shown to dissolve in the β-Zn4Sb3phase upon spark plasma sintering and thermocycling. β-Zn4+xSb3 solid solution depletion of interstitial zinc atoms or ZnSb phase precipitation upon thermocycling increase the thermal conductivity and reduce the thermoelectric efficiency of the material. The Zn4.1Sb3 composition has shown high thermoelectric efficiency, the 715 K ZT being ∼1.23 and 1.18 before and after thermocycling, respectively.

New Directions for Thermoelectrics: A Roadmap from High‐Throughput Materials Discovery to Advanced Device Manufacturing

Thermoelectric materials, which can convert waste heat into electricity or act as solid‐state Peltier coolers, are emerging as key technologies to address global energy shortages and environmental sustainability. However, discovering materials with high thermoelectric conversion efficiency is a complex and slow process. The emerging field of high‐throughput material discovery demonstrates its potential to accelerate the development of new thermoelectric materials combining high efficiency and low cost. The synergistic integration of high‐throughput material processing and characterization techniques with machine learning algorithms can form an efficient closed‐loop process to generate and analyze broad datasets to discover new thermoelectric materials with unprecedented performances. Meanwhile, the recent development of advanced manufacturing methods provides exciting opportunities to realize scalable, low‐cost, and energy‐efficient fabrication of thermoelectric devices. This review provides an overview of recent advances in discovering thermoelectric materials using high‐throughput methods, including processing, characterization, and screening. Advanced manufacturing methods of thermoelectric devices are also introduced to realize the broad impacts of thermoelectric materials in power generation and solid‐state cooling. In the end, this article also discusses the future research prospects and directions.

Development of the high temperature PbLi experimental facility for CFETR

Chinese Fusion Engineering and Test Reactor (CFETR) aims to demonstrate the fusion energy production up to 200MW, and finally reach commercial electricity power level 1GW. As one key component, the blanket is in charge of tritium breeding, neutron shielding and energy conversion. The liquid breeder blanket has many important advantages of simpler structure, tritium extraction and fuel replenishment online, as well as the high thermoelectric conversion efficiency. Moreover, the supercritical carbon dioxide (S-CO2) cOoled Lithium-Lead (COOL) blanket has been proposed for CFETR. However, the key issue of MagnetoHydroDynamics (MHD) needs further investigation, especially for the experiments. Therefore, the high temperature PbLi experimental loop is under development, which mainly includes three systems of PbLi, oil and water. The main components include the mechanical pump, main heater, cold trap as well as the superconducting magnet. At the test section, the mass flow rate, temperature and magnetic intensity will be up to 32 kg/s, 700 °C and 3T, respectively. In addition, the ultrasonic doppler velocimeter and potential probe instruments will be adopted to obtain the flow field. The main goal is to establish flow and heat transfer models, which are the critical input for the liquid breeder blanket design and optimization.

Cold Sintering Mediated Engineering of Polycrystalline SnSe with High Thermoelectric Efficiency.

Despite the attractive thermoelectric properties in single crystals, the fabrication of high-performance polycrystalline SnSe by a cost-effective strategy remains challenging. In this study, we prepare the undoped SnSe ceramic with remarkable thermoelectric efficiency by the combination of a cold sintering process (CSP) and thermal annealing. The high sintering pressure during CSP induces not only highly oriented grains but also a high concentration of lattice dislocations and stacking faults, which leads to large lattice strain that can shorten the phonon relaxation time. Meanwhile, the thermal annealing breaks the highly resistive SnOx layers at grain boundaries, which improves the electrical conductivity and power factor. In addition, the grain growth during annealing further turns the broken SnOx layers into nanoparticles, which further lowers the thermal conductivity by enhanced scattering. As a result, a peak ZT of 1.3 at 890 K and a high average ZT of 0.69 are achieved in the polycrystalline SnSe, suggesting great potential in mid-temperature power generation. This work may pave the way for the mass production of SnSe-based ceramics for thermoelectric devices.

Polytelluride square planar chain-induced anharmonicity results in ultralow thermal conductivity and high thermoelectric efficiency in Al2Te5 monolayers.

Two-dimensional (2D) metal chalcogenides provide rich ground for the development of nanoscale thermoelectrics, although achieving optimal thermoelectric efficiency is still a challenge. Here, we leverage the unique chemistry of tellurium (Te), renowned for its hypervalent bonding and catenation abilities, to tackle this challenge as manifested in Al2Te3 and Al2Te5 monolayers. While the former forms a straightforward covalent Al-Te network, the latter adopts a more intricate bonding mechanism, enabled by eccentric features of Te chemistry, to maintain charge balance. In Al2Te5, a square planar chain (SPC) known as polytelluride [Te3]2- is neutralized by the covalently bonded [Al2Te2]2+ framework. The hypervalent nature of Te results in bizarre Born effective charges of 7 and -4 for adjacent Te atoms within the square planar chain, a feature that induces significant anharmonicity in Al2Te5 monolayers. Enhanced anharmonic lattice vibrations and the accordion pattern bestow glass-like, strongly anisotropic thermal conductivity to the Al2Te5 monolayer. The calculated κL values of 1.8 and 0.5 W m-1 K-1 along the a- and b-axes at 600 K are one order of magnitude lower than those of Al2Te3, and even lower than monolayers that contain heavy cations like Bi2Te3. Moreover, the tellurium chain dominates the valence band maximum and conduction band minimum of Al2Te5, leading to a high valley degeneracy of 10, and thus a high power factor and figure of merit (zT). Using rigorous first-principles calculations of electron relaxation time, the estimated hole-doped and electron-doped zT of, respectively, 1.5 and 0.5 at 600 K is achieved for Al2Te5. The pioneering zT of Al2Te5 compared to that of Al2Te3 is rooted merely in its amorphous-like lattice thermal transport and its polytelluride chain. These findings underscore the importance of aluminum telluride and polymeric-based inorganic compounds as practical and cost-effective thermoelectric materials, pending further experimental validation.

High density lath twins lead to high thermoelectric conversion efficiency in Bi2Te3 modules.

Thermoelectric (TE) generators based on bismuth telluride (Bi2Te3) are recognized as a credible solution for low-grade heat harvesting. In this study, an combinative doping strategy of both the donor (Ag) and the acceptor (Ga) in Ag9GaTe6 as dopants is developed to modulate the microstructure and improve the ZT value of p-type Bi0.4Sb1.6Te3. Specifically, the distribution of Ag and Ga in the matrix synergistically introduces multiple phonon scattering centers including lath twins, triple junction boundaries, and Sb-rich nanoprecipitates, leading to an obviously suppressed lattice thermal conductivity of 0.50 W m-1 K-1 at 300 K. At the same time, such unique microstructures of lath twins synergistically enhance the room-temperature power factor to 48.8 μW cm-1 K-2 and improve the Vickers hardness to 0.90 GPa. Consequently, a high ZT of 1.40 at 350 K and ZTave of 1.24 (300-500 K) are achieved in the Bi0.4Sb1.6Te3 + 0.03 wt% Ag9GaTe6 sample. Based on that, a competitive conversion efficiency of 6.5% at ΔT = 200 K is obtained in the constructed 17-couple TE module, which exhibits no significant change in the output property after 30 thermal cycle tests benefiting from the stable microstructure.

Achieving high thermoelectric conversion efficiency in Bi2Te3-based stepwise legs through bandgap tuning and chemical potential engineering.

In this study, we show that the energy conversion efficiency in thermoelectric (TE) devices can be effectively improved through simultaneous optimization of carrier concentration, bandgap tuning, and fabrication of stepwise legs. n- and p-type Bi2Te3-based materials were selected as examples for testing the proposed approach. At first, the Boltzmann transport theory was employed to predict the optimal temperature-dependent carrier concentration for high thermoelectric performance over a broad temperature range. Then, the synthesized n-Bi2Te3-xSex and p-Bi2-xSbxTe3 solid solutions were tested to evaluate their suitability for fabricating the stepwise thermoelectric legs. The output energy characteristics of the designed TE devices were estimated using numerical modeling employing the finite element method. The theoretical simulation revealed an improvement in the conversion efficiency between the best homogeneous and stepwise TE legs from 8.8% to 10.1% and from 9.9% to 10.8% in p-type and n-type legs, respectively, which is much higher than the efficiency of the industrial thermoelectric modules (3-6%). The measured conversion efficiency of the fabricated n- and p-type stepwise legs reached very high values of 9.3% and 9.0%, respectively, at the relatively small temperature gradient of 375 K. This work suggests carrier concentration and bandgap engineering accompanied by the stepwise leg approach as powerful methods for achieving high energy conversion efficiency in thermoelectric converters.

Lattice thermal conductivity and thermoelectric properties of two-dimensional honeycomb monolayer of CdO

The lattice thermal conductivity of the CdO monolayer was investigated by density functional theory in combination with Boltzmann transport theory and it was estimated about 3.346 Wm−1K−1 at T = 300 K. Comparing this result with the one reported for the bulk CdO, it was revealed that the lattice thermal conductivity of the monolayer is lower than the bulk CdO. The lower lattice thermal conductivity of the CdO monolayer was attributed to the lower phonon lifetime and phonon group velocity in comparison to the bulk counterpart. Considering the lower lattice thermal conductivity of the monolayer, higher thermoelectric efficiency was estimated in comparison with the reported efficiency for the bulk CdO. At T = 900 K, the maximum zT = 0.76 can be found in p-type for the hole concentrations of 7.2 × 1012 cm−2.

Wide-temperature-range thermoelectric n-type Mg3(Sb,Bi)2 with high average and peak zT values

Mg3(Sb,Bi)2 is a promising thermoelectric material suited for electronic cooling, but there is still room to optimize its low-temperature performance. This work realizes >200% enhancement in room-temperature zT by incorporating metallic inclusions (Nb or Ta) into the Mg3(Sb,Bi)2-based matrix. The electrical conductivity is boosted in the range of 300–450 K, whereas the corresponding Seebeck coefficients remain unchanged, leading to an exceptionally high room-temperature power factor >30 μW cm−1 K−2; such an unusual effect originates mainly from the modified interfacial barriers. The reduced interfacial barriers are conducive to carrier transport at low and high temperatures. Furthermore, benefiting from the reduced lattice thermal conductivity, a record-high average zT > 1.5 and a maximum zT of 2.04 at 798 K are achieved, resulting in a high thermoelectric conversion efficiency of 15%. This work demonstrates an efficient nanocomposite strategy to enhance the wide-temperature-range thermoelectric performance of n-type Mg3(Sb,Bi)2, broadening their potential for practical applications.

Thermoelectric enhancement of a parallel double quantum dot system connecting to Luttinger liquid leads

In this work, we study the thermoelectric properties of the parallel-coupled double quantum dot connected to Luttinger liquid (LL) leads. By applying nonequilibrium Green's function methods, the expressions of the electron current, heat currents, and transport coefficients are derived. We mainly focus on the effect of intralead Coulomb interaction and the spatial asymmetry of the system. Various causes for the enhancement of the thermoelectric efficiency are investigated. We find that Coulomb interactions in the LL not only enhance quantum interference but also considerably enhance thermoelectric effects. For moderately strong intralead interaction, the figure of merit can be considerably high and reach over 60 in the case of weakly coupled to LL leads and detuning of the energy levels, while in the case of strongly coupled to LL leads and the two aligned levels, the figure of merit approaches 8. The quantum interference induced by the Coulomb interaction yields a very high thermoelectric efficiency when the intralead interaction is very strong. These results may provide a design rule for the development of high-efficiency thermoelectric devices and facilitate optimization of device performance.

Simultaneously Enhanced Energy Harvesting and Storage Performance Achieved by 3D Mix‐Phase Mose2‐Nise/NF

AbstractAs an energy harvesting device, the newly emerged thermocell has attracted great interest. However, it requires an additional energy storage device to complete a functional recycling system. As the core part of energy harvesting and storage devices, the design of electrodes with both high thermoelectric and electrochemical conversion efficiencies is particularly important. Herein, a high‐performance thermocell and supercapacitor device are constructed by employing the same mix‐phase MoSe2‐NiSe/NF electrode for both energy harvesting and storage. The thermocell exhibits an enhanced Seebeck coefficient of −1.69 mV K−1 and a superior output of 0.58 mW m−2 K−2 for low‐grade heat harvesting. Meanwhile, the supercapacitor device shows a great energy density of 54 Wh kg−1 at a power density of 806 W kg−1 and excellent cycling stability with a 92.8% retention rate after 50 000 cycles. This work offers a universal approach for the rational design of synergistic electrode materials to simultaneously achieve high‐energy harvesting and storage devices and lays a foundation for the recycling system of thermoelectric harvesting, conversion, and storage.

Structural and thermoelectric properties of MoSe2/CNT nanocomposites

Two-dimensional (2D) materials have emerged as a focus of research on energy conversion in recent years owing to their high thermal and thermoelectric efficiency. The authors of this study investigate the impact of carbon nanotubes (CNTs) on the structural, morphological, and thermoelectric properties of molybdenum diselenide (MoSe2). X-ray diffraction (XRD), Raman spectroscopy, Energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses were used to characterize the nanocomposites. The results showed that the layers of MoSe2 surrounded the CNTs and carrier transport occurred from MoSe2 to CNTs. The conductivity of the nanocomposite samples was significantly enhanced by incorporating the CNTs, which are known as mobility boosters. The thermoelectric power factor was 3.6 times higher than that of the pristine sample at ambient temperature. However, the random orientation of the CNTs in the nanocomposite at temperatures above 370 K led to high scattering at the interface that hindered the flow of current and reduced the mean free path of the carriers. Moreover, disordered grain boundaries and defects within the CNTs contributed to increased scattering at higher temperatures, and increased the power factor of the pristine MoSe2 by only 1.25 times. The results of this study demonstrated the potential of MoSe2/CNT nanocomposites for use in thermoelectric applications.

Technologies for manufacturing of Bi-Te-based thermoelectric materials

Bismuth-Telluride(Bi-Te)-based alloys are well-known for their high thermoelectric conversion efficiency, especially near room temperature, making them ideal for applications in solid-state refrigeration and power generation from waste heat. However, to expand their applications further, it is essential to improve their performance and reliability. To achieve these goals, recent research has been dedicated to developing processing technologies that can concurrently enhance the thermoelectric and mechanical properties. This is particularly crucial because the manufacturing process for these materials is intricate and demands precise parameter control to ensure the production of high-quality products. This review offers a comprehensive overview of the process technology employed in manufacturing Bi-Te-based thermoelectric materials, alongside introducing a cutting-edge near net shape hot extrusion technique recently developed for their production.

Decorated dislocations lead to dynamically optimized thermoelectric performance in N-type PbTe

A high thermoelectric energy conversion efficiency requires a large power factor and a low thermal conductivity over a broad temperature range. Optimizing the temperature-dependent carrier concentration and introducing structural defects are effective methods to realize these goals. In this work, we demonstrate that Ag-decorated dislocations can facilitate the dissolution of dopants into the PbTe matrix at elevated temperatures to optimize the carrier concentration in conjunction with the static doping effect of Sb. These spatially aligned and chemically decorated dislocations strongly scatter medium-to low-frequency phonons even at a rather low number density on the order of 1010 cm−2. Moreover, these dislocations show little scattering effect on electrons, maintaining a high carrier mobility. As a consequence, a maximum thermoelectric figure-of-merit, zT, of 1.5 at 750 K and an excellent average zT value of 1.1 between 300 and 800 K are obtained in Sb and dilute Ag2Te co-doped n-type PbTe. This work demonstrates that decorated dislocation networks could optimize the electrical and thermal transport properties of thermoelectrics in a wide temperature window.

Comparative analysis on high-efficiency energy conversion system with different working mediums matched with small lead-cooled fast reactor

Nuclear energy is developing toward miniaturization, high security, and efficiency. A new compact and high-efficiency energy conversion system is being developed to match the integrated and natural-circulated lead-cooled fast reactor. This energy conversion system uses a closed Brayton cycle instead of a steam Rankine cycle for its high thermoelectric conversion efficiency and simple and compact cycle arrangement. A recompression cycle is adopted to solve the heat exchanger pinch point problem while maintaining a relatively simple and compact cycle arrangement. Many mediums are used in the various Brayton cycles, including carbon dioxide (CO2), air, nitrogen, and helium, for which qualitative, but rare quantitative, assessments have been performed. In this study, systematical analysis and quantitative comparison are performed. The efficiency of the system is investigated using various typical working mediums at various split and compression ratios within the parameters of the system. According to various comparisons, the highest system conversion efficiency of CO2 in recompression Brayton cycles is 39.36% within the working temperature range of 15–560 °C under three pressure conditions (8 MPa, 13 MPa, 20 MPa), while the efficiencies of air, nitrogen, and helium are only 32.74%, 32.77%, and 32.48%, respectively. However, the efficiency of these last three working mediums will be higher under the optimal conditions of a simple Brayton cycle, which are 32.97%, 33.22%, and 33.59%, respectively. Finally, this paper proposes an energy conversion system scheme for a lead-cooled fast reactor with supercritical carbon dioxide (S–CO2) as the working fluid, a compression ratio of 2.5, a split ratio of 0.65, a maximum temperature of 560 °C, a maximum pressure of 20 MPa, and a system efficiency of 39.36%.

Chemical Doping of Organic and Coordination Polymers for Thermoelectric and Spintronic Applications: A Theoretical Understanding.

ConspectusThe controlled doping of organic semiconductors (OSCs) is crucial not only for improving the performance of electronic and optoelectronic devices but also for enabling efficient thermoelectric conversion and spintronic applications. The mechanism of doping for OSCs is fundamentally different from that of their inorganic counterparts. In particular, the interplay between dopants and host materials is complicated considering the low dielectric constant, strong lattice-charge interaction, and flexible nature of materials. Recent experimental breakthroughs in the molecular design of dopants and the precise doping with high spatial resolution call for more profound understandings as to how the dopant interacts with the charge introduced to OSCs and how the admixture of dopants alters the electronic properties of host materials before one can exploit controllable doping to realize desired functionalities.By employing state-of-the-art computational tools, we revealed the effects of doping in representative and emerging organic and coordination polymers aiming toward thermoelectric and spintronic applications. We showed that dopants and hosts should be taken as an integrated system, and the type of charge-transfer interaction between them is the key for spin polarization. First, we found doping-induced modifications to the electronic band in a potassium-doped coordination polymer, an n-type thermoelectric material. The charge localization due to the Coulomb interaction between the completely ionized dopant and the injected charge on the polymer backbone and also the polaron band formation at low doping levels are responsible for the nonmonotonic temperature dependence of the conductivity and Seebeck coefficient observed in recent experiments. The mechanistic insights gained from these results have provided important guidelines on how to control the doping level and working temperature to achieve a high thermoelectric conversion efficiency. Next, we demonstrated that the ionized dopants scatter charge carriers via screened Coulomb interactions, and it may become a dominant scattering mechanism in doped polymers. After incorporating the ionized dopant scattering mechanism in PEDOT:Tos, a p-type thermoelectric polymer, we were able to reproduce the measured Seebeck coefficient-electrical conductivity relationship spanning a wide range of doping levels, highlighting the importance of ionized dopant scattering in charge transport.In the two cases described above, charge injection is enabled by integral charge transfer between the dopant and host polymers. In a third example, we showed that a novel type of stacked two-dimensional polymer, conjugated covalent organic frameworks (COFs) with closed-shell electronic structures, can be spin polarized by iodine doping via fractional charge transfer even at high doping levels. We then manifested that magnetization can be attained in nonmagnetic materials lacking metal d electrons and further designed two new COFs with tunable spintronic structure and magnetic interactions after the iodine doping. These findings have suggested a practical route to enable spin polarization in nonradical materials by chemical doping via orbital hybridization, which holds great promise for flexible spintronic applications.