The rhombohedralα-GeTe can be approximated as a slightly distorted rock-salt structure along its[111]direction and possesses superb thermoelectric performance.However,the role of such a ferroelectric-like structural ...The rhombohedralα-GeTe can be approximated as a slightly distorted rock-salt structure along its[111]direction and possesses superb thermoelectric performance.However,the role of such a ferroelectric-like structural distortion on its transport properties remains unclear.Herein,we performed a systematic study on the crystal structure and electronic band structure evolutions of Ge_(1-x)Sn_(x)Te alloys where the degree of ferroelectric distortion is continuously tuned.It is revealed that the band gap is maximized while multiple valence bands are converged at x=0.6,where the ferroelectric distortion is the least but still works.Once undistorted,the band gap is considerably reduced,and the valence bands are largely separated again.Moreover,near the ferro-to-paraelectric phase transition Curie temperature,the lattice thermal conductivity reaches its minima because of significant lattice softening enabled by ferroelectric instability.We predict a peak ZT value of 2.6 at 673 K inα-GeTe by use of proper dopants which are powerful in suppressing the excess hole concentrations but meanwhile exert little influence on the ferroelectric distortion.展开更多
Materials with both large magnetocaloric response and high thermoelectric performance are of vital importance for all-solid-state thermoelectromagnetic cooling.These two properties,however,hardly coexist in single pha...Materials with both large magnetocaloric response and high thermoelectric performance are of vital importance for all-solid-state thermoelectromagnetic cooling.These two properties,however,hardly coexist in single phase materials except previously reported hexagonal Cr_(1-x)Te half metal where a relatively high magnetic entropy change(-△S_(M))of~2.4 J·kg^(-1)·K^(-1)@5 T and a moderate thermoelectric figure of merit(ZT)of~1.2×10^(-2)@300 K are simultaneously recorded.Herein we aim to increase the thermoelectric performance of Cr_(1-x)Te by compositing with semiconducting Ag_(2)Te.It is discovered that the in-situ synthesis of Cr_(1-x)Te/Ag_(2)Te composites by reacting their constitute elements above melting temperatures is unsuccessful because of strong phase competition.Specifically,at elevated temperatures(T>800 K),Cr_(1-x)Te has a much lower deformation energy than Ag_(2)Te and tends to become more Cr-deficient by capturing Te from Ag_(2)Te.Therefore,Ag is insufficiently reacted and as a metal it deteriorates ZT.We then rationalize the synthesis of Cr_(1-x)Te/Ag_(2)Te composites by ex-situ mix of the pre-prepared Cr_(1-x)Te and Ag_(2)Te binary compounds followed by densification at a low sintering temperature of 573 K under a pressure of 3.5 GPa.We show that by compositing with 7 mol%Ag_(2)Te,the Seebeck coefficient of Cr_(1-x)Te is largely increased while the lattice thermal conductivity is considerably reduced,leading to 72%improvement of ZT.By comparison,-△S_(M)is only slightly reduced by 10%in the composite.Our work demonstrates the potential of Cr_(1-x)Te/Ag_(2)Te composites for thermoelectromagnetic cooling.展开更多
Garnet-type solid-state electrolytes(SSEs)are a remarkable Li-ion electrolyte for the realization of next-generation all-solid-state lithium batteries due to their excellent stability against Li metal as well as high ...Garnet-type solid-state electrolytes(SSEs)are a remarkable Li-ion electrolyte for the realization of next-generation all-solid-state lithium batteries due to their excellent stability against Li metal as well as high ionic conductivities at room temperature.However,garnet electrolytes always contain undesired and hardly removable Li_(2)CO_(3) contaminations that have persistently large resistance and unstable interface contact with Li metal.This is a critical bottleneck for the practical application of garnet electrolytes.Here,we design a novel strategy to completely root out Li_(2)CO_(3) both inside and on the surface of garnet.This is achieved by a so-called double replacement reaction between Li_(2)CO_(3) and SiO_(2) during one-step hot press process for garnet electrolyte densification.It leads to in-situ transformation of LixSiOy(LSO)mostly locating around the grain boundaries of garnet.Due to the higher ion conductivity and better electrochemistry stability of LSO than Li_(2)CO_(3),the modified garnet electrolyte shows much improved electrochemical performance.Moreover,the wettability between modified garnet electrolyte and lithium metals was significantly enhanced in the absence of surface Li_(2)CO_(3).As a proof of concept,an assembled Li symmetric cell with modified garnet electrolyte displays a high critical current density(CCD)of 0.7 mA cm^(-2)and a low interfacial impedance(5Ωcm^(2))at 25℃.These results indicate that the upcycling of Li_(2)CO_(3)is a promising strategy to well-address the degradation and interfacial issue associated with garnet electrolytes.展开更多
Miniaturization of efficient thermoelectric(TE)devices has long been hindered by the weak mechanical strength and insufficient heat-to-electricity conversion efficiency of zone-melted(ZM)ingots.Here,we successfully pr...Miniaturization of efficient thermoelectric(TE)devices has long been hindered by the weak mechanical strength and insufficient heat-to-electricity conversion efficiency of zone-melted(ZM)ingots.Here,we successfully prepared a robust high-performance p-type Bi_(0.4)Sb_(1.6)Te_(3.72)bulk alloy by combining an ultrafast thermal explosion reaction with the spark plasma sintering(TER-SPS)process.It is observed that the introduced excess Te not only enhances the(00l)-oriented texture to ensure an outstanding power factor(PF)of 5 mW m^(−1)K^(−2),but also induces extremely high-density line defects of up to 10^(11)–10^(12)cm^(−2).Benefiting from such heavily dense line defects,the enhancement of the electronic thermal conductance from the increased electron mobility is fully compensated by the stronger phonon scattering,leading to an evident net reduction in total thermal conductivity.As a result,a superior ZT value of~1.4 at 350 K is achieved,which is 40%higher than that of commercial ZM ingots.Moreover,owing to the strengthening of grain refinement and highdensity line defects,the mechanical compressive stress reaches up to 94 MPa,which is 154%more than that of commercial single crystals.This research presents an effective strategy for the collaborative optimization of the texture,TE performance,and mechanical strength of Bi2Te3-based materials.As such,the present study contributes significantly to the future commercial development of miniature TE devices.展开更多
Although traditional ferroelectric materials are usually dielectric and nonconductive,GeTe is a typical ferroelectric semiconductor,possessing both ferroelectric and semiconducting properties.GeTe is also a widely stu...Although traditional ferroelectric materials are usually dielectric and nonconductive,GeTe is a typical ferroelectric semiconductor,possessing both ferroelectric and semiconducting properties.GeTe is also a widely studied thermoelectric material,whose performance has been optimized by doping with various elements.However,the impact of the ferroelectric domains on the thermoelectric properties remains unclear due to the difficulty to directly observe the ferroelectric domains and their evolutions under actual working conditions where the material is exposed to high temperatures and electric currents.Herein,based on in-situ investigations of the ferroelectric domains and domain walls in both pure and Sb-doped GeTe crystals,we have been able to analyze the dynamic evolution of the ferroelectric domains and domain walls,exposed to an electric field and temperature.Local structural heterogeneities and nano-sized ferroelectric domains are generated due to the interplay of the Sb^(3+)dopant and the Ge-vacancies,leading to the increased number of charged domain walls and a much improved thermoelectric performance.This work reveals the fundamental mechanism of ferroelectric thermoelectrics and provides insights into the decoupling of previously interdependent properties such as thermo-power and electrical conductivity.展开更多
基金the financial support from the National Natural Science Foundation of China(Grant No.52171221)the National Key Research and Development Program of China(Grant No.2019YFA0704900)the support from the Core Facility of Wuhan University for their assistance with EPMA analysis
文摘The rhombohedralα-GeTe can be approximated as a slightly distorted rock-salt structure along its[111]direction and possesses superb thermoelectric performance.However,the role of such a ferroelectric-like structural distortion on its transport properties remains unclear.Herein,we performed a systematic study on the crystal structure and electronic band structure evolutions of Ge_(1-x)Sn_(x)Te alloys where the degree of ferroelectric distortion is continuously tuned.It is revealed that the band gap is maximized while multiple valence bands are converged at x=0.6,where the ferroelectric distortion is the least but still works.Once undistorted,the band gap is considerably reduced,and the valence bands are largely separated again.Moreover,near the ferro-to-paraelectric phase transition Curie temperature,the lattice thermal conductivity reaches its minima because of significant lattice softening enabled by ferroelectric instability.We predict a peak ZT value of 2.6 at 673 K inα-GeTe by use of proper dopants which are powerful in suppressing the excess hole concentrations but meanwhile exert little influence on the ferroelectric distortion.
基金Project supported by the National Key Research and Development Program of China(Grant No.2019YFA0704900)the National Natural Science Foundation of China(Grant No.52171221)。
文摘Materials with both large magnetocaloric response and high thermoelectric performance are of vital importance for all-solid-state thermoelectromagnetic cooling.These two properties,however,hardly coexist in single phase materials except previously reported hexagonal Cr_(1-x)Te half metal where a relatively high magnetic entropy change(-△S_(M))of~2.4 J·kg^(-1)·K^(-1)@5 T and a moderate thermoelectric figure of merit(ZT)of~1.2×10^(-2)@300 K are simultaneously recorded.Herein we aim to increase the thermoelectric performance of Cr_(1-x)Te by compositing with semiconducting Ag_(2)Te.It is discovered that the in-situ synthesis of Cr_(1-x)Te/Ag_(2)Te composites by reacting their constitute elements above melting temperatures is unsuccessful because of strong phase competition.Specifically,at elevated temperatures(T>800 K),Cr_(1-x)Te has a much lower deformation energy than Ag_(2)Te and tends to become more Cr-deficient by capturing Te from Ag_(2)Te.Therefore,Ag is insufficiently reacted and as a metal it deteriorates ZT.We then rationalize the synthesis of Cr_(1-x)Te/Ag_(2)Te composites by ex-situ mix of the pre-prepared Cr_(1-x)Te and Ag_(2)Te binary compounds followed by densification at a low sintering temperature of 573 K under a pressure of 3.5 GPa.We show that by compositing with 7 mol%Ag_(2)Te,the Seebeck coefficient of Cr_(1-x)Te is largely increased while the lattice thermal conductivity is considerably reduced,leading to 72%improvement of ZT.By comparison,-△S_(M)is only slightly reduced by 10%in the composite.Our work demonstrates the potential of Cr_(1-x)Te/Ag_(2)Te composites for thermoelectromagnetic cooling.
基金financial support from the National Natural Science Foundation of China(Grant No.11804261)National Key Research and Development Program of China(Grant No.2019YFA0704900)。
文摘Garnet-type solid-state electrolytes(SSEs)are a remarkable Li-ion electrolyte for the realization of next-generation all-solid-state lithium batteries due to their excellent stability against Li metal as well as high ionic conductivities at room temperature.However,garnet electrolytes always contain undesired and hardly removable Li_(2)CO_(3) contaminations that have persistently large resistance and unstable interface contact with Li metal.This is a critical bottleneck for the practical application of garnet electrolytes.Here,we design a novel strategy to completely root out Li_(2)CO_(3) both inside and on the surface of garnet.This is achieved by a so-called double replacement reaction between Li_(2)CO_(3) and SiO_(2) during one-step hot press process for garnet electrolyte densification.It leads to in-situ transformation of LixSiOy(LSO)mostly locating around the grain boundaries of garnet.Due to the higher ion conductivity and better electrochemistry stability of LSO than Li_(2)CO_(3),the modified garnet electrolyte shows much improved electrochemical performance.Moreover,the wettability between modified garnet electrolyte and lithium metals was significantly enhanced in the absence of surface Li_(2)CO_(3).As a proof of concept,an assembled Li symmetric cell with modified garnet electrolyte displays a high critical current density(CCD)of 0.7 mA cm^(-2)and a low interfacial impedance(5Ωcm^(2))at 25℃.These results indicate that the upcycling of Li_(2)CO_(3)is a promising strategy to well-address the degradation and interfacial issue associated with garnet electrolytes.
基金financially supported by the National Key Research and Development Program of China (2018YFB0703600)the National Natural Science Foundation of China (51772232)+1 种基金the 111 Project of China (B07040)Wuhan Frontier Project on Applied Research Foundation (2019010701011405)
文摘Miniaturization of efficient thermoelectric(TE)devices has long been hindered by the weak mechanical strength and insufficient heat-to-electricity conversion efficiency of zone-melted(ZM)ingots.Here,we successfully prepared a robust high-performance p-type Bi_(0.4)Sb_(1.6)Te_(3.72)bulk alloy by combining an ultrafast thermal explosion reaction with the spark plasma sintering(TER-SPS)process.It is observed that the introduced excess Te not only enhances the(00l)-oriented texture to ensure an outstanding power factor(PF)of 5 mW m^(−1)K^(−2),but also induces extremely high-density line defects of up to 10^(11)–10^(12)cm^(−2).Benefiting from such heavily dense line defects,the enhancement of the electronic thermal conductance from the increased electron mobility is fully compensated by the stronger phonon scattering,leading to an evident net reduction in total thermal conductivity.As a result,a superior ZT value of~1.4 at 350 K is achieved,which is 40%higher than that of commercial ZM ingots.Moreover,owing to the strengthening of grain refinement and highdensity line defects,the mechanical compressive stress reaches up to 94 MPa,which is 154%more than that of commercial single crystals.This research presents an effective strategy for the collaborative optimization of the texture,TE performance,and mechanical strength of Bi2Te3-based materials.As such,the present study contributes significantly to the future commercial development of miniature TE devices.
基金supported by the National Natural Science Foundation of China(52072282)the National Key Research and Development Program of China(2019YFA0704900)performed at the Nanostructure Research Center(NRC),which is supported by the Fundamental Research Funds for the Central Universities(WUT:2021Ⅲ016GX)。
文摘Although traditional ferroelectric materials are usually dielectric and nonconductive,GeTe is a typical ferroelectric semiconductor,possessing both ferroelectric and semiconducting properties.GeTe is also a widely studied thermoelectric material,whose performance has been optimized by doping with various elements.However,the impact of the ferroelectric domains on the thermoelectric properties remains unclear due to the difficulty to directly observe the ferroelectric domains and their evolutions under actual working conditions where the material is exposed to high temperatures and electric currents.Herein,based on in-situ investigations of the ferroelectric domains and domain walls in both pure and Sb-doped GeTe crystals,we have been able to analyze the dynamic evolution of the ferroelectric domains and domain walls,exposed to an electric field and temperature.Local structural heterogeneities and nano-sized ferroelectric domains are generated due to the interplay of the Sb^(3+)dopant and the Ge-vacancies,leading to the increased number of charged domain walls and a much improved thermoelectric performance.This work reveals the fundamental mechanism of ferroelectric thermoelectrics and provides insights into the decoupling of previously interdependent properties such as thermo-power and electrical conductivity.
