Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg...Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg_(3)Sb_(2)remains lower than 1,which is mainly attributed to its inferior electrical properties.Herein,we synergistically optimize the thermoelectric properties of p-type Mg_(3)Sb_(2)materials via codoping of Cd and Ag,which were synthesized by high-energy ball milling combined with hot pressing.It is found that Cd doping not only increases the carrier mobility of p-type Mg_(3)Sb_(2),but also diminishes its thermal conductivity(κ_(tot)),with Mg_(2.85)Cd_(0.5)Sb_(2)achieving a lowκtot value of∼0.67 W m^(−1)K^(−1)at room temperature.Further Ag doping elevates the carrier concentration,so that the power factor is optimized over the entire temperature range.Eventually,a peak zT of∼0.75 at 773 K and an excellent average zT of∼0.41 over 300−773 K are obtained in Mg_(2.82)Ag_(0.03)Cd_(0.5)Sb_(2),which are∼240%and∼490%higher than those of pristine Mg_(3.4)Sb_(2),respectively.This study provides an effective pathway to synergistically improve the thermoelectric performance of p-type Mg_(3)Sb_(2)by codoping Cd and Ag,which is beneficial to the future applications of Mg_(3)Sb_(2)-based thermoelectric materials.展开更多
Mg_(3)Sb_(2)-based thermoelectric materials have been the focus of widespread investigations as promising candidates for the harvesting of waste heat.Interface stability and service performance are key points for the ...Mg_(3)Sb_(2)-based thermoelectric materials have been the focus of widespread investigations as promising candidates for the harvesting of waste heat.Interface stability and service performance are key points for the commercial applications of these materials.We utilized Mg_(4.3)Sb_(3)Ni as a barrier layer to improve the thermal stability of Mg 3 Sb 2-based devices.However,its intrinsic high resistivity contributed nega-tively to the desired performance of the device.In this work,we investigated two other Mg-Sb-Ni ternary phases,MgSbNi and MgSbNi_(2),as new barrier layer materials to connect with Mg_(3.2)Sb_(2)Y_(0.05).The results show that the efficiency of the Mg_(1.2)SbNi/Mg_(3.2)Sb_(2)Y_(0.05)/Mg_(1.2)SbNi joint is increased by 33%relative to the higher Mg-content barriers due to lower resistivity.The system exhibited good interfacial compatibility and showed little change with aging at 673 K for 20 days.展开更多
P-type Mg_(3)Sb_(2)-based Zintls have attracted considerable interest in the thermoelectric(TE)field due to their environmental friendliness and low cost.However,compared to their n-type counterparts,they show relativ...P-type Mg_(3)Sb_(2)-based Zintls have attracted considerable interest in the thermoelectric(TE)field due to their environmental friendliness and low cost.However,compared to their n-type counterparts,they show relatively low TE performance,limiting their application in TE devices.In this work,we simultaneously introduce Bi alloying at Sb sites and Ag doping at Mg sites into the Mg_(3)Sb_(2)to coopera-tively optimize the electrical and thermal properties for the first time,acquiring the highest ZT value of∼0.85 at 723 K and a high average ZT of 0.39 in the temperature range of 323-723 K in sample Mg_(2.94)Ag_(0.06)Sb_(1.9)Bi_(0.1).The first-principle calculations show that the codoping of Ag and Bi can shift the Fermi level into the valence band and narrow the band gap,resulting in the increased carrier concentration from 3.50×10^(17)cm^(-3)in the reference Mg 3 Sb 0.9 Bi 0.1 to∼7.88×10^(19)cm^(-3)in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.As a result,a remarkable power factor of∼778.9μW m^(-1)K^(-2)at 723 K is achieved in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.Meanwhile,a low lattice thermal conductivity of∼0.48 W m^(-1)K^(-1)at 723 K is also obtained with the help of phonon scattering at the distorted lattice,point defects,and nano-precipitates in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.The synergistic effect of using the multi-element co-doping/-alloying to optimize electrical properties in Mg_(3)Sb_(2)holds promise for further improving the TE performance of Zintl phase materials or even others.展开更多
The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehy...The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.展开更多
Reducing thermal conductivity while avoiding adverse interfacial reactions during sintering is crucial for improving the thermoelectric performance of Bi_(2)Te_(3)based composites.Inert ceramic nanoparticles are good ...Reducing thermal conductivity while avoiding adverse interfacial reactions during sintering is crucial for improving the thermoelectric performance of Bi_(2)Te_(3)based composites.Inert ceramic nanoparticles are good candidates for achieving this goal.In this study,we designed and prepared a series of p-type Bi_(0.5)Sb_(1.5)Te_(3)nanocomposites decorated with Y_(2)O_(3)ceramic nanoparticles via ball-milling dispersion and spark-plasma sintering.Owing to the chemical stability of the ceramics,no traces of atomic doping or interfacial reactions were observed.Transport measurements revealed that the Y_(2)O_(3)nanoparticles distributed along the grain boundaries acted as energy-dependent carrier-filtering centers to improve the scattering parameter and Seebeck coefficient,contributing to the elevated power factor even with a decreased electrical conductivity.Moreover,the incorporated Y_(2)O_(3)nanoparticles and various defect structures they induced effectively strengthened the phonon scattering and suppressed the lattice thermal conductivity.Consequently,a peak figure of merit(ZT)of 1.23 at 313 K was achieved for 0.4%Y_(2)O_(3)/Bi_(0.5)Sb_(1.5)Te_(3),which is 13%higher than that of the matrix.In addition,the Vickers hardness of the composite material was 35%higher than that of the matrix.This study demonstrates the effectiveness of ceramic nanoparticles in synergistic ally improving the thermoelectric and mechanical properties,which may be further extended to other thermoelectric systems.展开更多
Ce2[Zr_(1-x)(Mg_(1/3)Sb_(2/3))_(x)]_(3)(MoO_(4))_(9)(0.02≤x≤0.10)ceramics were prepared by the traditional solid-state method.A single phase,belonging to the space group of R3c,was detected by using X-ray diffractio...Ce2[Zr_(1-x)(Mg_(1/3)Sb_(2/3))_(x)]_(3)(MoO_(4))_(9)(0.02≤x≤0.10)ceramics were prepared by the traditional solid-state method.A single phase,belonging to the space group of R3c,was detected by using X-ray diffraction at the sintering temperatures ranging from 700 to 850℃.The microstructures of samples were examined by applying scanning electron microscopy(SEM).The crystal structure refinement of these samples was investigated in detail by performing the Rietveld refinement method.The intrinsic properties were calculated and explored via far-infrared reflectivity spectroscopy.The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by Phillips-van Vechten-Levine(P-V-L)theory.Ce_(2)[Zr_(0.94)(Mg_(1/3)Sb_(2/3))_(0.06)]_(3)(Mo0_(4))_(9)ceramics with excellent dielectric properties were sintered at 725℃for 6 h(εr=10.37,Q×f=71,748 GHz,andτf=-13.6 ppm/℃,εr is the dielectric constant,τf is the quality factor,and rf is the temperature coefficient of resonant frequency).展开更多
Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials with a reasonably low thermal conductivity.However,their electrical transport property is usually limited by the low carrier concentration.Mg_(3)Sb_(2) ...Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials with a reasonably low thermal conductivity.However,their electrical transport property is usually limited by the low carrier concentration.Mg_(3)Sb_(2) has a multi-valley conduction band with a six-fold degeneracy,benefiting n-type thermoelectric performance.Recently,n-type Y-doped Mg_(3)Sb_(1.5)Bi_(0.5) and Sc-doped Mg_(3)Sb_(2)-Mg_(3)Bi_(2) alloys show a large figure of merit(ZT).In this paper,the doping effect of group-3 and chalcogen elements on the electronic structures and electrical transport properties of Mg_(3)Sb_(2) was investigated via the first-principles calculations.Chalcogen elements have a slight effect on the electronic structure,and Te-doped Mg_(3)Sb_(2) shows better normalized power factors in both the out-of-plane and in-plane directions,compared to the Sdoped and Se-doped systems.Distinctly different doping effects appear in Mg_(3)Sb_(2) doped with group-3 elements.A increased density of states near the bottom of the conduction band can be induced by Sc or Y.Sc-doped and Y-doped Mg_(3)Sb_(2) show higher normalized power factors along the in-plane direction than those doped with chalcogens.展开更多
Mg_(3)Sb_(2)-based thermoelectric materials have poor electrical conductivity which is the key to limit thermoelectric performance that need to be solved.Herein we tuned the carrier concentration of Mg_(3)Sb_(2)-based...Mg_(3)Sb_(2)-based thermoelectric materials have poor electrical conductivity which is the key to limit thermoelectric performance that need to be solved.Herein we tuned the carrier concentration of Mg_(3)Sb_(2)-based materials via Ag doping at the Mg sites(at two distinct crystallographic sites)to enhance the electrical performance.Mg_(3-x)Ag_(x)Sb_(2)(0≤x≤0.05)has been prepared successfully by vacuum suspension smelting plus Spark Plasma Sintering technique.Using the vacuum suspension smelting plus Spark Plasma Sintering method,we proved that Ag doping can precisely tune the electrical transport properties and accordingly enhance the power factor.Moreover,the Ag doping leads to a low lattice thermal conductivity due to phonons scattering,and the maximal thermoelectric figure of merit ZT for Mg_(3-x)Ag_(x)Sb_(2)reaches 0.66 at 773 K.展开更多
Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials through n-type doping in Mg-rich growth conditions to overcome their intrinsic p-type behavior.First principle calculations are employed to investigate ...Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials through n-type doping in Mg-rich growth conditions to overcome their intrinsic p-type behavior.First principle calculations are employed to investigate the dopant formation energy and electronic structures of Y-doped Mg_(3)Sb_(2).Results indicate that the Y atom is more favorable for substitution at the cation site.Simultaneously,the flattened band structure and increased density of state near the Fermi level of Y-doped Mg_(3)Sb_(2) indicate an enhanced electronic transport performance.The carrier concentration rises to 5.31×10^(19) cm^(-3) at room temperature,resulting in a significant increased power factor for Mg_(3.17)Y_(0.03)Sb_(2).The available optimization of electrical transport contributes to excellent thermoelectric performance,and a peak ZT~0.83 at 773 K was achieved for Y concentration x=0.03 in Mg_(3.2-x)Y_(x)Sb_(2).This work provides an alternative measure for optimizing the thermoelectric performance of n-type Mg_(3)Sb_(2) alloys by cation site doping.展开更多
Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing ...Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing to its rich chemistry and structural complexity.However,it hardly achieves high ZT values throughout the medium temperature range.Herein,by increasing the sintering temperature as much as possible,we successfully increased the average grain size of the compound by 15 times,and the grain boundary scattering was manipulated to obtain high carrier mobility of up to 180 cm^(2)V^(-1)s^(-1).Simultaneously,we optimized the Mg content for ultralow lattice thermal conductivity.We first doped the Mg_(3)Sb_(2)-based materials with boron for higher sintering temperature,good thermal stability,and higher hardness.The synergistic optimization of electrical and thermal transport resulted in excellent ZT values(0.62 at 300 K,1.81 at 773 K)and an average ZT of 1.4(from300 to 773 K),which are higher than the state-of-the-art values for n-type thermoelectric materials,demonstrating a high potential in device applications.展开更多
Magnesium-based materials have been regarded as promising candidates for large-scale,high-efficiency thermoelectric applications,owing to their excellent dimensionless figure of merit,high abundance,and low cost.In th...Magnesium-based materials have been regarded as promising candidates for large-scale,high-efficiency thermoelectric applications,owing to their excellent dimensionless figure of merit,high abundance,and low cost.In this review,we comprehensively summarize the recent advances of Mg-based thermoelectrics,including Mg_(2)X(X=Si,Ge,Sn),Mg3(Sb,Bi)_(2),andα-MgAgSb,from both material and device level.Their electrical and thermal transport properties are first elucidated based on the crystallographic characteristics,band structures,and phonon dispersions.We then review the optimization strategies towards higher thermoelectric performance,as well as the device applications of Mg-based thermoelectric materials and the related engineering issues.By highlighting the challenges and possible solutions in the end,this review intends to offer perspectives on the future research work to further enhance the performance of Mg-based materials for practical applications.展开更多
基金financially supported by the National Natural Science Foundation of China (Grant No. 52071041, 11874356, 51802034)supported by the Key Research Program of Frontier Sciences, CAS (Grant No.QYZDB-SSW-SLH016)
文摘Mg_(3)Sb_(2)has attracted intensive attention as a typical Zintl-type thermoelectric material.Despite the exceptional thermoelectric performance in n-type Mg_(3)Sb_(2),the dimensionless figure of merit(zT)of p-type Mg_(3)Sb_(2)remains lower than 1,which is mainly attributed to its inferior electrical properties.Herein,we synergistically optimize the thermoelectric properties of p-type Mg_(3)Sb_(2)materials via codoping of Cd and Ag,which were synthesized by high-energy ball milling combined with hot pressing.It is found that Cd doping not only increases the carrier mobility of p-type Mg_(3)Sb_(2),but also diminishes its thermal conductivity(κ_(tot)),with Mg_(2.85)Cd_(0.5)Sb_(2)achieving a lowκtot value of∼0.67 W m^(−1)K^(−1)at room temperature.Further Ag doping elevates the carrier concentration,so that the power factor is optimized over the entire temperature range.Eventually,a peak zT of∼0.75 at 773 K and an excellent average zT of∼0.41 over 300−773 K are obtained in Mg_(2.82)Ag_(0.03)Cd_(0.5)Sb_(2),which are∼240%and∼490%higher than those of pristine Mg_(3.4)Sb_(2),respectively.This study provides an effective pathway to synergistically improve the thermoelectric performance of p-type Mg_(3)Sb_(2)by codoping Cd and Ag,which is beneficial to the future applications of Mg_(3)Sb_(2)-based thermoelectric materials.
基金supported by the National Science Foundation of China(Grant No.52202277)the Special Project of Science and Technology Cooperation and Exchange of Shanxi Province(Grant No.202104041101007).
文摘Mg_(3)Sb_(2)-based thermoelectric materials have been the focus of widespread investigations as promising candidates for the harvesting of waste heat.Interface stability and service performance are key points for the commercial applications of these materials.We utilized Mg_(4.3)Sb_(3)Ni as a barrier layer to improve the thermal stability of Mg 3 Sb 2-based devices.However,its intrinsic high resistivity contributed nega-tively to the desired performance of the device.In this work,we investigated two other Mg-Sb-Ni ternary phases,MgSbNi and MgSbNi_(2),as new barrier layer materials to connect with Mg_(3.2)Sb_(2)Y_(0.05).The results show that the efficiency of the Mg_(1.2)SbNi/Mg_(3.2)Sb_(2)Y_(0.05)/Mg_(1.2)SbNi joint is increased by 33%relative to the higher Mg-content barriers due to lower resistivity.The system exhibited good interfacial compatibility and showed little change with aging at 673 K for 20 days.
基金supported by the National Natural Science Foundation of China(Grant Nos.U21A2054,52273285,52061009,52262032)the National Key Research and Development Program of China(No.2022YFE0119100)the Guangxi Science and Technology Planning Project(Grant No.AD21220056).
文摘P-type Mg_(3)Sb_(2)-based Zintls have attracted considerable interest in the thermoelectric(TE)field due to their environmental friendliness and low cost.However,compared to their n-type counterparts,they show relatively low TE performance,limiting their application in TE devices.In this work,we simultaneously introduce Bi alloying at Sb sites and Ag doping at Mg sites into the Mg_(3)Sb_(2)to coopera-tively optimize the electrical and thermal properties for the first time,acquiring the highest ZT value of∼0.85 at 723 K and a high average ZT of 0.39 in the temperature range of 323-723 K in sample Mg_(2.94)Ag_(0.06)Sb_(1.9)Bi_(0.1).The first-principle calculations show that the codoping of Ag and Bi can shift the Fermi level into the valence band and narrow the band gap,resulting in the increased carrier concentration from 3.50×10^(17)cm^(-3)in the reference Mg 3 Sb 0.9 Bi 0.1 to∼7.88×10^(19)cm^(-3)in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.As a result,a remarkable power factor of∼778.9μW m^(-1)K^(-2)at 723 K is achieved in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.Meanwhile,a low lattice thermal conductivity of∼0.48 W m^(-1)K^(-1)at 723 K is also obtained with the help of phonon scattering at the distorted lattice,point defects,and nano-precipitates in sample Mg 2.94 Ag 0.06 Sb 0.9 Bi 0.1.The synergistic effect of using the multi-element co-doping/-alloying to optimize electrical properties in Mg_(3)Sb_(2)holds promise for further improving the TE performance of Zintl phase materials or even others.
基金the financial support provided by the Natural Science Foundations in Hebei Province(No.E2018201235)Baoding Science and Technology Planning Project(No.2074P019)+2 种基金Higher Education in Hebei Province School Science and Technology Research Project(No.QN2019209)Horizontal project(horizontal 20230048)2022 Hebei Province and Hebei University College Students Innovation and Entrepreneurship Training Program(Nos.2022265 and 2022266)。
文摘The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.
基金financially supported by the National Natural Science Foundation of China(Nos.11834012 and 52130203)。
文摘Reducing thermal conductivity while avoiding adverse interfacial reactions during sintering is crucial for improving the thermoelectric performance of Bi_(2)Te_(3)based composites.Inert ceramic nanoparticles are good candidates for achieving this goal.In this study,we designed and prepared a series of p-type Bi_(0.5)Sb_(1.5)Te_(3)nanocomposites decorated with Y_(2)O_(3)ceramic nanoparticles via ball-milling dispersion and spark-plasma sintering.Owing to the chemical stability of the ceramics,no traces of atomic doping or interfacial reactions were observed.Transport measurements revealed that the Y_(2)O_(3)nanoparticles distributed along the grain boundaries acted as energy-dependent carrier-filtering centers to improve the scattering parameter and Seebeck coefficient,contributing to the elevated power factor even with a decreased electrical conductivity.Moreover,the incorporated Y_(2)O_(3)nanoparticles and various defect structures they induced effectively strengthened the phonon scattering and suppressed the lattice thermal conductivity.Consequently,a peak figure of merit(ZT)of 1.23 at 313 K was achieved for 0.4%Y_(2)O_(3)/Bi_(0.5)Sb_(1.5)Te_(3),which is 13%higher than that of the matrix.In addition,the Vickers hardness of the composite material was 35%higher than that of the matrix.This study demonstrates the effectiveness of ceramic nanoparticles in synergistic ally improving the thermoelectric and mechanical properties,which may be further extended to other thermoelectric systems.
基金supported by the National Natural Science Foundation(No.51972143).
文摘Ce2[Zr_(1-x)(Mg_(1/3)Sb_(2/3))_(x)]_(3)(MoO_(4))_(9)(0.02≤x≤0.10)ceramics were prepared by the traditional solid-state method.A single phase,belonging to the space group of R3c,was detected by using X-ray diffraction at the sintering temperatures ranging from 700 to 850℃.The microstructures of samples were examined by applying scanning electron microscopy(SEM).The crystal structure refinement of these samples was investigated in detail by performing the Rietveld refinement method.The intrinsic properties were calculated and explored via far-infrared reflectivity spectroscopy.The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by Phillips-van Vechten-Levine(P-V-L)theory.Ce_(2)[Zr_(0.94)(Mg_(1/3)Sb_(2/3))_(0.06)]_(3)(Mo0_(4))_(9)ceramics with excellent dielectric properties were sintered at 725℃for 6 h(εr=10.37,Q×f=71,748 GHz,andτf=-13.6 ppm/℃,εr is the dielectric constant,τf is the quality factor,and rf is the temperature coefficient of resonant frequency).
基金supported by the Research Grants Council of Hong Kong(17200017 and 17300018)the National Natural Science Foundation of China(51706192 and 11874313)+1 种基金the Zhejiang Provincial Natural Science Foundation(LR19A040001)the Science,Technology and Innovation Commission of Shenzhen Municipality(JCYJ20180307154619840).
文摘Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials with a reasonably low thermal conductivity.However,their electrical transport property is usually limited by the low carrier concentration.Mg_(3)Sb_(2) has a multi-valley conduction band with a six-fold degeneracy,benefiting n-type thermoelectric performance.Recently,n-type Y-doped Mg_(3)Sb_(1.5)Bi_(0.5) and Sc-doped Mg_(3)Sb_(2)-Mg_(3)Bi_(2) alloys show a large figure of merit(ZT).In this paper,the doping effect of group-3 and chalcogen elements on the electronic structures and electrical transport properties of Mg_(3)Sb_(2) was investigated via the first-principles calculations.Chalcogen elements have a slight effect on the electronic structure,and Te-doped Mg_(3)Sb_(2) shows better normalized power factors in both the out-of-plane and in-plane directions,compared to the Sdoped and Se-doped systems.Distinctly different doping effects appear in Mg_(3)Sb_(2) doped with group-3 elements.A increased density of states near the bottom of the conduction band can be induced by Sc or Y.Sc-doped and Y-doped Mg_(3)Sb_(2) show higher normalized power factors along the in-plane direction than those doped with chalcogens.
基金This work is supported by National Natural Science Foundation of China(Grant No.51371010,51572066,50801002)the Beijing Municipal Natural Science Foundation(Grant No.2112007).
文摘Mg_(3)Sb_(2)-based thermoelectric materials have poor electrical conductivity which is the key to limit thermoelectric performance that need to be solved.Herein we tuned the carrier concentration of Mg_(3)Sb_(2)-based materials via Ag doping at the Mg sites(at two distinct crystallographic sites)to enhance the electrical performance.Mg_(3-x)Ag_(x)Sb_(2)(0≤x≤0.05)has been prepared successfully by vacuum suspension smelting plus Spark Plasma Sintering technique.Using the vacuum suspension smelting plus Spark Plasma Sintering method,we proved that Ag doping can precisely tune the electrical transport properties and accordingly enhance the power factor.Moreover,the Ag doping leads to a low lattice thermal conductivity due to phonons scattering,and the maximal thermoelectric figure of merit ZT for Mg_(3-x)Ag_(x)Sb_(2)reaches 0.66 at 773 K.
基金supported by National Natural Science Foundation of China,China(Grant Nos.51371010,51572066 and 50801002)Beijing Municipal Natural Science Foundation,China(Grant No.2112007)the Fundamental Research Funds for the Central Universities,China(PXM2019-014204-500032).
文摘Mg_(3)Sb_(2)-based alloys are promising thermoelectric materials through n-type doping in Mg-rich growth conditions to overcome their intrinsic p-type behavior.First principle calculations are employed to investigate the dopant formation energy and electronic structures of Y-doped Mg_(3)Sb_(2).Results indicate that the Y atom is more favorable for substitution at the cation site.Simultaneously,the flattened band structure and increased density of state near the Fermi level of Y-doped Mg_(3)Sb_(2) indicate an enhanced electronic transport performance.The carrier concentration rises to 5.31×10^(19) cm^(-3) at room temperature,resulting in a significant increased power factor for Mg_(3.17)Y_(0.03)Sb_(2).The available optimization of electrical transport contributes to excellent thermoelectric performance,and a peak ZT~0.83 at 773 K was achieved for Y concentration x=0.03 in Mg_(3.2-x)Y_(x)Sb_(2).This work provides an alternative measure for optimizing the thermoelectric performance of n-type Mg_(3)Sb_(2) alloys by cation site doping.
基金supported by the National Natural Science Foundation of China(51771065 and 51871082)the Natural Science Foundation of Heilongjiang Province of China(ZD2020E003)。
文摘Thermoelectric devices require thermoelectric materials with high figure-of-merit(ZT)values in the operating temperature range.In recent years,the Zintl phase compound,n-Mg_(3)Sb_(2),has received much attention owing to its rich chemistry and structural complexity.However,it hardly achieves high ZT values throughout the medium temperature range.Herein,by increasing the sintering temperature as much as possible,we successfully increased the average grain size of the compound by 15 times,and the grain boundary scattering was manipulated to obtain high carrier mobility of up to 180 cm^(2)V^(-1)s^(-1).Simultaneously,we optimized the Mg content for ultralow lattice thermal conductivity.We first doped the Mg_(3)Sb_(2)-based materials with boron for higher sintering temperature,good thermal stability,and higher hardness.The synergistic optimization of electrical and thermal transport resulted in excellent ZT values(0.62 at 300 K,1.81 at 773 K)and an average ZT of 1.4(from300 to 773 K),which are higher than the state-of-the-art values for n-type thermoelectric materials,demonstrating a high potential in device applications.
基金financial support from the National Natural Science Foundation of China(Grant Nos.52125103,52071041,12104071,11874356,U21A2054)。
文摘Magnesium-based materials have been regarded as promising candidates for large-scale,high-efficiency thermoelectric applications,owing to their excellent dimensionless figure of merit,high abundance,and low cost.In this review,we comprehensively summarize the recent advances of Mg-based thermoelectrics,including Mg_(2)X(X=Si,Ge,Sn),Mg3(Sb,Bi)_(2),andα-MgAgSb,from both material and device level.Their electrical and thermal transport properties are first elucidated based on the crystallographic characteristics,band structures,and phonon dispersions.We then review the optimization strategies towards higher thermoelectric performance,as well as the device applications of Mg-based thermoelectric materials and the related engineering issues.By highlighting the challenges and possible solutions in the end,this review intends to offer perspectives on the future research work to further enhance the performance of Mg-based materials for practical applications.
