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摘要

热电材料可以实现热能和电能间的直接相互转换, 在半导体制冷和热能回收方面有着重要应用. Zintl相热电材料由电负性差异较大的阴阳离子组成, 其输运特征符合“声子玻璃, 电子晶体”的概念, 因此受到了广泛的研究, 特别是具有二维共价键子结构Zintl相热电材料凭借优异的电性能更是被寄予厚望. 本文综述了具有二维共价键子结构的典型Zintl相热电材料, 梳理了研究最广且性能突出的CaAl ₂Si ₂结构1-2-2型、原胞内原子较多本征低热导率的9–4+ x–9型、具有天然空位而本征热导率极低的2-1-2型、以及电性能相对较好的ZrBeSi结构1-1-1型Zintl相的研究进展; 其中还特别总结了性能优异的Mg ₃Sb ₂基n型Zintl材料的研究发展. 本文概括总结了每种体系近年来的研究进展及性能调控方法, 讨论了进一步优化其热电性能的可能策略, 并对其未来发展进行了展望.

关键词:

Abstract

Thermoelectric materials can realize the direct conversion between thermal energy and electrical energy, and thus having important applications in semiconductor refrigeration and heat recovery. Zintl phase is composed of highly electronegative cations and anions, which accords with the concept of “phonon glass, electron crystal” (PGEC). Thermoelectric properties of Zintl phase have attracted extensive interest, among which the two-dimensional (2D) covalent bond structure featured Zintl phases have received more attention for their outstanding electrical properties. In this review, Zintl phase materials with two-dimensional covalent bond substructures are reviewed, including 1-2-2-type, 9–4+ x–9-type, 2-1-2-type and 1-1-1-type Zintl phase. The 1-2-2-type Zintl phase is currently the most widely studied and best-performing Zintl material. It is worth mentioning that the maximum ZTvalue for the Mg ₃Sb ₂-based n-type Zintl material with the CaAl ₂Si ₂structure has been reported to reach 1.85, and the average ZTvalue near room temperature area also reaches 1.4. The 9–4+ x–9-type Zintl material with a mass of atoms in unit cell contributes to lower thermal conductivity thus relatively high ZTvalue. The 2-1-2-type Zintl material has extremely low thermal conductivity due to the intrinsic vacancies, which has been developing in recent years. The 1-1-1-type Zintl material with the same ZrBeSi structure as the 2-1-2-type Zintl material, shows better electrical transport performance. In sum, this review summarizes the recent progress and optimization methods of those typical Zintl phases above. Meanwhile, the future optimization and development of Zintl phase with two-dimensional covalent bond substructures are also prospected.

Keywords:

thermoelectric materials/
Zintl phase/
2-dimensional covalent bond substructure

作者及机构信息

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2.

通信作者:谈小建,tanxiaojian@nimte.ac.cn; 帅晶,shuaij3@mail.sysu.edu.cn

基金项目:国家自然科学基金 (批准号: 52002413, 21875273)、广东省自然科学基金(批准号: 2021A1515010612)、浙江省自然科学基金杰出青年项目(批准号: LR21E020002)和中国科学院青年创新促进会(批准号: 2019298)资助的课题.

Authors and contacts

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Corresponding author:Tan Xiao-Jian,tanxiaojian@nimte.ac.cn; Shuai Jing,shuaij3@mail.sysu.edu.cn

Funds:Project supported by the National Natural Science Foundation of China (Grant Nos. 52002413, 21875273), the Natural Science Foundation of Guangdong Province, China (Grant No. 2021A1515010612), the Natural Science Foundation of Zhejiang Province, China (Grant No. LR21E020002), and Youth Innovation Promotion Association CAS (Grant No. 2019298).

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施引文献

下载: 全尺寸图片幻灯片

时间	材料	Ρ/(mΩ·cm)	S/ (μV·K^–1)	κ/(W·m^–1·K^–1)	ZT	T/ K	ZT_RT
2005	Ca_0.25Yb_0.75Zn₂Sb₂^[36]	3.7	170	1.4	0.56	773	0.08
2007	BaZn₂Sb₂^[38]	6.1	185	1.25	0.33	673	0.05
2008	YbZn_1.9Mn_0.1Sb₂^[57]	1.5	150	1.6	0.65	726	0.05
2008	EuZn₂Sb₂^[58]	1.8	180	1.45	0.9	713	0.16
2009	YbCd_1.6Zn_0.4Sb₂^[46]	1.66	180	1.1	1.2	650	0.2
2010	Yb_0.6Ca_0.4Cd₂Sb₂^[37]	4.4	240	0.9	0.96	700	0.14
2010	Yb_0.75Eu_0.25Cd₂Sb₂^[59]	4	240	1	0.97	650	0.18
2010	EuZn_1.8Cd_0.2Sb₂^[47]	2	200	1.4	1.06	650	0.18
2011	YbCd_1.85Mn_0.15Sb₂^[60]	5.7	245	0.6	1.14	650	0.17
2012	YbMg₂Bi₂^[39]	5	180	1.8	0.44	650	0.07
2014	Yb_0.99Zn₂Sb₂^[61]	1.3	160	1.7	0.85	800	0.05
2016	YbCd_1.9Mg_0.1Sb₂^[40]	3.3	230	1.02	1.08	650	0.2
2016	Ca_0.5Yb_0.5Mg₂Bi₂^[49]	2.8	187	1.08	1	873	0.1
2016	Ca_0.995Na_0.005Mg₂Bi_1.98^[54]	3	200	1.25	0.9	873	0.05
2016	Eu_0.2Yb_0.2Ca_0.6Mg₂Bi₂^[8]	3.5	215	0.92	1.3	875	0.25
2018	YbCd_1.5Zn_0.5Sb₂^[34]	1.7	172	1.2	1.26	700	0.18
2018	Yb_0.96Ba_0.04Cd_1.5Zn_0.5Sb₂^[34]	2	185	0.94	1.3	700	0.18
2019	Ba_0.7975Yb_0.2Na_0.0025Cd₂Sb₂^[41]	4.1	210	0.81	0.93	700	0.1
2019	EuCd_1.4Zn_0.6Sb₂^[42]	3.5	220	1	0.96	700	0.18
2020	Ca_0.65Yb_0.35Mg_1.9Zn_0.1Bi_1.98^[43]	2.63	185	1.04	1	773	0.2
2020	YbMg₂Bi_1.58Sb_0.4^[44]	4.1	219	1	1.05	873	0.14
2020	Sm_0.25Yb_0.375Eu_0.375Mg₂Bi_1.99^[45]	3.7	197	0.9	0.9	773	0.18
2020	(Yb_0.9Mg_0.1)Mg_0.8Zn_1.198Ag_0.002Sb₂^[21]	4.75	257	0.74	1.5	773	0.28

下载: 导出CSV

时间	材料	ρ/(mΩ·cm)	S/(μV·K^–1)	κ/(W·m^–1·K^–1)	ZT	T/K	ZT_RT
2006	Mg₃Sb₂^[83]	29	288	1.2	0.21	875	0.001
2013	Mg₃Bi_0.2Sb_1.8^[76]	40	400	0.58	0.6	750	0.01
2014	Mg₃Pb_0.2Sb_1.8^[48]	28.6	280	0.28	0.84	773	0.03
2015	Mg_2.9875Na_0.0125Sb₂^[66]	5.4	200	0.95	0.6	773	0.03
2017	Mg_2.985Ag_0.015Sb₂^[22]	9	205	0.65	0.51	725	0.08
2016	Mg_3.2Sb_1.5Bi_0.49Te_0.01^[67]	5	–286	0.79	1.51	716	0.2
2016	Mg₃Sb_1.48Bi_0.48Te_0.04^[53]	10	–205	0.73	1.6	750	0.6
2017	Mg_3.05Nb_0.15Sb_1.5Bi_0.49Te_0.01^[9]	4.35	–277	0.84	1.57	700	0.31
2017	Mg_3.1Co_0.1Sb_1.5Bi_0.49Te_0.01^[69]	5.1	–295	0.78	1.7	773	0.4
2018	Mg_3.15Mn_0.05Sb_1.5Bi0_.49Te_0.01^[10]	4.5	–302	0.79	1.85	723	0.42
2019	Mg_3+δSb_1.5Bi_0.49Te_0.01:Mn_0.01^[78]	4.5	–290	0.9	1.6	773	0.65
2019	Mg_3.05SbBi_0.97Te_0.03^[74]	1.7	–202	0.92	1.31	500	0.71
2019	Mg_3.02Y_0.02Sb_1.5Bi_0.5^[11]	4.2	–270	0.76	1.8	773	0.2
2020	Mg_3.2Sb_1.99Te_0.01+GNP^[23]	6.4	–320	0.74	1.7	750	0.18
2021	Mg_3.17B_0.03Sb_1.5Bi0_.49Te_0.01^[12]	5.4	–296	0.69	1.81	773	0.62

下载: 导出CSV

时间	材料	ρ/(mΩ·cm)	S/(μV·K^–1)	κ/(W·m^–1·K^–1)	ZT	T/K	ZT_RT
2014	Yb₉Mn_4.2Sb₉^[87]	7.9	185	0.58	0.7	950	0.035
2015	Eu₉Cd_3.75Ag_1.42Sb₉^[91]	2.0	85	1.0	0.32	750	0.03
2016	Ca₉Zn_4.35Cu_0.15Sb₉^[89]	3.0	140	0.8	0.72	873	0.1
2017	Ca₉Zn_4.6Sb₉^[27]	11.0	270	0.48	1.1	873	0.1
2019	Ca_6.75Eu_2.25Zn_4.7Sb₉^[28]	5.55	200	0.53	1.05	773	0.21
2021	Sr₉Mg_4.45Bi₉^[90]	3.75	135	0.65	0.57	773	0.14 (323 K)

下载: 导出CSV

时间	材料	ρ/(mΩ·cm)	S/(μV·K^–1)	κ/(W·m^–1·K^–1)	ZT	T/K	ZT_RT
2017	Yb₂CdSb₂^[92]	5	155	0.52	0.2	523	0.23
2017	Yb_1.64Eu_0.36CdSb₂^[92]	3.5	170	0.6	0.7	523	0.26
2018	Eu₂ZnSb₂^[25]	24.4	290	0.42	0.6	723	0.14
2018	Eu₂Zn_0.98Sb₂^[25]	8	220	0.48	1	823	0.22
2020	Eu₂Zn_0.97Ag_0.06Sb₂^[24]	10	220	0.43	0.93	823	0.2
2020	Eu₂Zn_0.95Ag_0.06Sb₂^[24]	5.3	194	0.5	1.1	823	0.2

下载: 导出CSV

时间	材料	ρ/(mΩ·cm)	S/(μV·K^–1)	κ/(W·m^-1·K^–1)	ZT	T/K	ZT_RT
2018	Ca_0.85La_0.15Ag_0.89Sb^[106]	1.85	120	1.3	0.52	860	0.07
2018	Ca_0.55Sr_0.3La_0.15Ag_0.89Sb^[106]	1.6	125	1.0	0.7	823	0.1
2020	SrAgSb^[26]	0.95	114	2.2	0.5	773	0.07
2020	Sr_1.01AgSb^[26]	1.27	125	1.7	0.58	773	0.1
2020	EuCuSb^[26]	0.64	83	2.9	0.3	773	0.03
2020	EuAgSb^[26]	0.74	90	2.4	0.35	773	0.05

下载: 导出CSV

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