CN107359232A - A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material and the method that the thermoelectric material is prepared by element substitution - Google Patents

A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material and the method that the thermoelectric material is prepared by element substitution Download PDF

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CN107359232A
CN107359232A CN201710519492.9A CN201710519492A CN107359232A CN 107359232 A CN107359232 A CN 107359232A CN 201710519492 A CN201710519492 A CN 201710519492A CN 107359232 A CN107359232 A CN 107359232A
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sbs
cubic
emission
sintering
base thermoelectricity
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CN107359232B (en
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刘丙国
汪舰
胡保付
徐坚
杜保立
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Henan University of Technology
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Henan University of Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth

Abstract

The invention provides a kind of Emission in Cubic Cu3SbS3Base thermoelectricity material, chemical general formula Cu3Sb1‑xAxS3, wherein A is cobalt and/or nickel, and x is 0.025~0.200, by using the element substitution Sb elements such as Ni, Co, has synthesized the stable Cu of structure, macroscopic property3Sb1‑ xAxS3Cubic crystal structure.Its preparation method mainly includes the following steps that：1) dispensing：According to Cu3Sb1‑xAxS3The ratio of middle each element weigh needed for the copper of quality, antimony, cobalt (nickel), sulphur as reaction raw materials, wherein x=0.025~0.200；2) high-energy ball milling：Step 1) the reaction raw materials are subjected to high-energy ball milling under inert gas atmosphere；3) it is densified：Powder obtained by high-energy ball milling is subjected to discharge plasma sintering or hot pressed sintering, obtains high-compactness, high performance Emission in Cubic Cu3SbS3Base thermoelectricity material block.Cu of the present invention3Sb1‑ xAxS3Thermoelectric material is the Emission in Cubic product of high-purity, and consistency is high, and thermodynamic property is stable, and thermoelectricity capability is excellent, and raw material sources are abundant cheap, and preparation technology feasibility is good, is easy to repeat.

Description

A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material and the thermoelectricity material is prepared by element substitution The method of material
Technical field
The invention belongs to new energy materialses field, and in particular to a kind of Emission in Cubic Cu3SbS3Base thermoelectricity material, and pass through Element substitution synthesis stable cubic phase Cu3SbS3The preparation method of base thermoelectricity material.
Background technology
Energy security is the important component of national security, using new energy conversion and recovery technology from primary energy Recovery section heat energy is to reduce the usage amounts such as oil, natural gas, alleviate China to external stone in caused waste heat during use The important channel of oily supply pressure.Thermoelectric power generation technology is to realize that heat energy and electric energy are direct using the Seebeck effects of semiconductor The new energy transformation technology of conversion, wherein being adapted to thermoelectric material (solar energy, underground heat, industry in terms of generating in medium temperature section Waste heat and residual heat of tail gas of automobile etc. recycle) there is important application prospect, it is the one kind for tackling global warming and energy shortage Important new energy transition material.Cu-Sb-S pyroelectric materials have nontoxic, cost relative to traditional tellurides thermoelectric material Many advantages, such as low and synthesis material easily obtains, the recent studies on being increasingly becoming required for today's society " low-carbon green " development trend One of focus.
Cu-Sb-S pyroelectric materials include four kinds of compounds, wherein Cu3SbS3.25Composition has optimal thermoelectricity capability.But During application and popularizations, the composition has the trend for decomposing slowly to copper-rich phase and poor copper phase at low temperature, seriously constrain this into The long service performance divided.Cu3SbS3Compound has and Cu3SbS3.25Similar chemical composition, structural research shows, the change Compound has three kinds of completely clear and definite compositions, Cu under low temperature3SbS3For orthorhombic phase, space group P212121；263K to 395K Between be monoclinic phase, space group P21/c；395K is to being another orthorhombic phase between fusing point, space group Pnma.
For needing the thermoelectric material of long-time non-stop run, the good heat between material and substrate, electrical contact It is one of indispensable condition.The phase transformation of thermoelectric material can all destroy the combination of material and substrate in any operation temperature area, so as to lead The failure of pyrogenicity electrical part.Conventional commercial thermoelectric material has stable chemical composition and crystal phase structure, therefore Cu3SbS3Chemical combination Thing seriously hinders it to turn into commercial thermoelectric material in 395 K phase transformation.In theory, in addition to three of the above rock-steady structure, Cu3SbS3Compound can also be formed and Cu3SbS3.25(tetrahedrite) similar metastable state cube phase structure.In the prior art, Zhong etc. uses solvent structure Cu3SbS3Nanometer rods, Maiello etc. are using two-step method (magnetron sputtering+sulfuration process) Cu has been synthesized in glass substrate3SbS3Film, but the two products therefrom is metastable state, therefore in heat treatment process or military service During structural phase transition from the opposite monocline of metastable state cube or orthogonal stable phase will inevitably occur, destroy material with Good contact between substrate, limit its application in thermoelectricity field.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of Emission in Cubic for above-mentioned the shortcomings of the prior art Cu3SbS3Base thermoelectricity material and preparation method thereof, i.e. selection use Co and/or Ni element substitutions Cu3SbS3Part Sb in compound Member usually stablizes its cubic structure, the Cu prepared3SbS3There is cubic phase crystal structure and stable heating power in mesophilic range Property is learned, and thermoelectricity capability is excellent, is Cu3SbS3Application of the compound in thermoelectricity field is laid a good foundation.
The present invention is to solve the problems, such as that used technical scheme set forth above is：
A kind of Cu3SbS3Base thermoelectricity material, is Emission in Cubic, and its chemical general formula is Cu3Sb1-xAxS3, wherein A be Co and/or Ni, x are 0.025~0.200.
Emission in Cubic Cu of the present invention3SbS3Base thermoelectricity material, its density are more than or equal to 4.85g/cm3(Emission in Cubic Cu3SbS3 Solid density is 5.10g/cm3), thermoelectricity capability index ZT is not small when 550-620K warm areas maximum is not less than 0.55,300K In 0.1.
Emission in Cubic Cu of the present invention3SbS3Base thermoelectricity material, its chemical composition are Cu3Sb0.90Co0.10S3When, density is 4.90g/cm3, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.65；Emission in Cubic Cu of the present invention3SbS3Base heat Electric material, its chemical composition are Cu3Sb0.90Ni0.10S3When, density 4.93g/cm3, thermoelectricity capability index ZT is in 550-620K Warm area maximum is up to 0.62.
Above-mentioned Emission in Cubic Cu3SbS3The preparation method of base thermoelectricity material, is mainly included the following steps that：
1) dispensing：According to Cu3Sb1-xAxS3The mol ratio of each element in chemical general formula, weigh elemental copper, antimony, A, sulfur powder As reaction raw materials, i.e. the ratio between amount of material of copper, antimony, A, sulphur is 3:(1-x):x:3, or in this stoichiometric proportion slightly about Fluctuation, fluctuating range are less than 2%, and wherein A is Co and/or Ni, x are 0.025~0.200；
2) high-energy ball milling：Step 1) the reaction raw materials are subjected to high-energy ball milling under inert gas atmosphere；
3) it is densified：Powder obtained by step 2) is densified using discharge plasma sintering or hot pressed sintering, obtained The single phase cubic phase Cu of High Density High Performance3SbS3Base thermoelectricity material block.
By such scheme, the step 1) copper, antimony, A, the ratio between the amount of material of sulphur are 3:(1-x):x:3, or it is chemical herein Metering is than neighbouring slight fluctuations, and fluctuating range is less than 2%, and wherein x is 0.05~0.1.
By such scheme, copper, antimony, cobalt, nickel, sulphur simple substance powder purity described in step 1) are not less than 99%, it is preferably to powder Last simple substance.
By such scheme, the High Energy Ball Milling Time described in step 2) is 15~30h.
By such scheme, the high-energy ball milling rotating speed described in step 2) is 350-650rpm.
By such scheme, the high-energy ball milling ratio of grinding media to material described in step 2) is 10~30.
By such scheme, the condition of the discharge plasma sintering described in step 3) is：Under vacuum or inert atmosphere, sintering pressure Power is not less than 20MPa, and sintering temperature is 350~520 DEG C, and sintering time is 1~30min；The condition of described hot pressed sintering is： Under vacuum or inert atmosphere, sintering pressure is not less than 20MPa, and sintering temperature is 370~540 DEG C, and sintering time is 10~ 120min。
Compared with prior art, the beneficial effects of the invention are as follows：
1st, Cu prepared by the present invention3SbS3Base thermoelectricity material, there is stable cube phase structure.Prepared by conventional method Cu3SbS3Material is monocline, and 395K nearby has monocline-orthohormbic structure phase transformation, has a strong impact on the long service of material Energy.The present invention is using Ni and Co displacements Cu3SbS3Part Sb in compound, change the valence link feature between zwitterion, make metastable State cubic structure becomes stable state cubic crystal structure, so as to obtain the stable high performance thermoelectric material of crystalline phase.
2nd, the present invention is using material process and technology of preparing ripe in industrial or laboratory, with copper, antimony, cobalt or nickel, Sulphur is raw material, and substitutional element Co and/or Ni is cheap relative to being replaced element sb element rich reserves, nontoxic, and Obtained Emission in Cubic Cu3SbS3Base thermoelectricity material, consistency is high, purity is high, Stability Analysis of Structures, and thermoelectricity capability is excellent, approaches or is better than Commercial tellurides thermoelectric material.
3rd, the raw materials used physicochemical properties of the present invention are stable, are easily obtained and lay in, and preparation process technique is simply controllable, Sintering method flexible and selectable, without special process and processing, and prepared Emission in Cubic Cu3SbS3Base thermoelectricity material thermodynamics Matter is stable, and thermoelectricity capability is excellent, is Cu3SbS3Application of the compound in thermoelectricity field is laid a good foundation.
Brief description of the drawings
Fig. 1 is the block Emission in Cubic Cu prepared by embodiment 13SbS3Base thermoelectricity material (discharge plasma sintering step it Powder x-ray diffraction collection of illustrative plates (XRD) afterwards), to embody products therefrom of the present invention and tetrahedrite (Cu3SbS3.25) with identical Cubic structure, the XRD spectrum of tetrahedrite is shown in figure.
Fig. 2 is the Emission in Cubic Cu prepared by embodiment 13SbS3The thermoelectricity capability figure of base thermoelectricity material.
Fig. 3 is the block Emission in Cubic Cu prepared by embodiment 23SbS3Base thermoelectricity material (discharge plasma sintering step it Powder x-ray diffraction collection of illustrative plates (XRD) afterwards), to embody products therefrom of the present invention and tetrahedrite (Cu3SbS3.25) with identical Cubic structure, the XRD spectrum of tetrahedrite is shown in figure.
Fig. 4 is the Emission in Cubic Cu prepared by embodiment 23SbS3The thermoelectricity capability figure of base thermoelectricity material.
Fig. 5 is the block Emission in Cubic Cu prepared by embodiment 33SbS3Base thermoelectricity material (discharge plasma sintering step it Powder x-ray diffraction collection of illustrative plates (XRD) afterwards), to embody products therefrom of the present invention and tetrahedrite (Cu3SbS3.25) with identical Cubic structure, the XRD spectrum of tetrahedrite is shown in figure.
Fig. 6 is the Emission in Cubic Cu prepared by embodiment 33SbS3The thermoelectricity capability figure of base thermoelectricity material.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not It is limited only to the following examples.
Embodiment 1
A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material, its preparation method comprise the following steps：
1) dispensing：According to Cu3Sb1-xAxS3The ratio of each element calculates the quality of each element in (A is Co or Ni), claims respectively As reaction raw materials, i.e. the ratio between amount of material of copper, antimony, cobalt or nickel, sulphur is 3 for copper, antimony, cobalt or the nickel of quality, sulphur needed for taking: (1-x):x:3, wherein x=0.10；The quality purity of copper is better than 99.5%, and the quality purity of antimony is better than 99.5%, and elemental sulfur is Analyze pure, simple substance cobalt (nickel) purity 99%；
2) mechanical alloying：Step 1) the reaction raw materials are poured into stainless steel jar mill, in inert gas shielding High-energy ball milling, rotational speed of ball-mill 450rpm, ratio of grinding media to material 20, Ball-milling Time 20h are carried out under atmosphere；
3) discharge plasma sintering：Powder obtained by step 2) is loaded in diameter 15mm graphite jigs, discharge etc. from Son sintering, sintering temperature are 400 DEG C, time 5min, pressure 35MPa, produce high-compactness Emission in Cubic Cu3SbS3Base thermoelectricity material Expect block.
In the present embodiment, Co or Ni is taken to carry out above-mentioned preparation process as A respectively.Wherein, when A is Ni, the high-compactness Emission in Cubic Cu3SbS3The chemical composition of base thermoelectricity material block is Cu3Sb0.90Ni0.10S3, density 4.93g/cm3；A is Co When, high-compactness Emission in Cubic Cu3SbS3The chemical composition of base thermoelectricity material block is Cu3Sb0.90Co0.10S3, density is 4.90g/cm3。
As shown in Figure 1：A is respectively Co or Ni, and gained thermoelectric material block is list after step 3) discharge plasma sintering Phase Emission in Cubic Cu3SbS3Compound, occurs without any miscellaneous peak, and initiation material is fully converted to target product Emission in Cubic Cu3SbS3Compound.
Emission in Cubic Cu obtained by the present embodiment3SbS3The thermoelectricity capability of base thermoelectricity material is shown in Fig. 2, is characterized with ZT values, step 3) Its chemical composition of gained thermoelectric material block is Cu after discharge plasma sintering3Sb0.90Co0.10S3When, thermoelectricity capability index ZT exists 550-620K warm areas maximum is up to 0.65；Its chemical composition of gained thermoelectric material block is after step 3) discharge plasma sintering Cu3Sb0.90Ni0.10S3When, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.62.
Embodiment 2
A kind of Emission in Cubic Cu3SbS3Base thermoelectricity material, its preparation method comprise the following steps：
1) dispensing：According to Cu3Sb1-xAxS3The ratio of each element calculates the quality of each element in (A=Co or Ni), claims respectively As reaction raw materials, i.e. the ratio between amount of material of copper, antimony, cobalt (nickel), sulphur is 3 for the copper of quality, antimony, cobalt (nickel), sulphur needed for taking: (1-x):x:3, wherein x=0.05, the quality purity of copper are better than 99.5%, and the quality purity of antimony is better than 99.5%, and elemental sulfur is Analyze pure, simple substance cobalt (nickel) purity 99%；
2) mechanical alloying：Step 1) the reaction raw materials are poured into stainless steel jar mill, in inert gas shielding High-energy ball milling, rotational speed of ball-mill 450rpm, ratio of grinding media to material 20, Ball-milling Time 20h are carried out under atmosphere；
3) discharge plasma sintering：Powder obtained by step 2) is loaded in diameter 15mm graphite jigs, discharge etc. from Son sintering, sintering temperature are 400 DEG C, time 5min, pressure 35MPa, produce high-compactness Emission in Cubic Cu3SbS3Base thermoelectricity material Expect block.When wherein A is Ni, high-compactness Emission in Cubic Cu3SbS3The chemical composition of base thermoelectricity material block is Cu3Sb0.95Ni0.05S3, density 4.94g/cm3；When A is Co, high-compactness Emission in Cubic Cu3SbS3Base thermoelectricity material block Chemical composition is Cu3Sb0.95Co0.05S3, density 4.90g/cm3。
As shown in Figure 3：A is respectively Co or Ni, and gained thermoelectric material block is list after step 3) discharge plasma sintering Phase Emission in Cubic Cu3SbS3Compound, occurs without any miscellaneous peak, and initiation material is fully converted to target product Emission in Cubic Cu3SbS3Change Compound.
Emission in Cubic Cu obtained by the present embodiment3SbS3The thermoelectricity capability of base thermoelectricity material is shown in Fig. 4, and its chemical composition is Cu3Sb0.95Co0.05S3When, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.62；Its chemical composition is Cu3Sb0.95Ni0.05S3When, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.60.
Embodiment 3
One kind prepares Emission in Cubic Cu3SbS3The method of base thermoelectricity material, comprises the following steps：
1) dispensing：According to Cu3Sb1-xAxS3The ratio of each element calculates the quality of each element in (A=Co or Ni), claims respectively As reaction raw materials, i.e. the ratio between amount of material of copper, antimony, cobalt (nickel), sulphur is 3 for the copper of quality, antimony, cobalt (nickel), sulphur needed for taking: (1-x):x:3, wherein x=0.20, the quality purity of copper are better than 99.5%, and the quality purity of antimony is better than 99.5%, and elemental sulfur is Analyze pure, simple substance cobalt (nickel) purity 99%；
2) mechanical alloying：Step 1) the reaction raw materials are poured into stainless steel jar mill, in inert gas shielding High-energy ball milling, rotational speed of ball-mill 350rpm, ratio of grinding media to material 15, Ball-milling Time 30h are carried out under atmosphere；
3) hot pressed sintering：Powder obtained by step 2) is loaded in diameter 15mm graphite jigs, carries out hot-pressing densification sintering, Sintering temperature is 5000 DEG C, time 20min, pressure 40MPa, produces high-compactness Emission in Cubic Cu3SbS3Base thermoelectricity material block Body.When wherein A is Ni, high-compactness Emission in Cubic Cu3SbS3The chemical composition of base thermoelectricity material block is Cu3Sb0.80Ni0.20S3, density 4.90g/cm3；When A is Co, high-compactness Emission in Cubic Cu3SbS3Base thermoelectricity material block Chemical composition is Cu3Sb0.80Co0.20S3, density 4.88g/cm3。
As shown in Figure 5：A is respectively Co or Ni, and gained thermoelectric material block is list after step 3) discharge plasma sintering Phase Emission in Cubic Cu3SbS3Compound, occurs without any miscellaneous peak, and initiation material is fully converted to target product Emission in Cubic Cu3SbS3Compound.
Emission in Cubic Cu obtained by the present embodiment3SbS3The thermoelectricity capability of base thermoelectricity material is shown in Fig. 6, and its chemical composition is Cu3Sb0.80Ni0.20S3When, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.58；Its chemical composition is Cu3Sb0.80Ni0.20S3When, thermoelectricity capability index ZT is in 550-620K warm areas maximum up to 0.56.
Described above is only the preferred embodiment of the present invention, it is noted that is come for one of ordinary skill in the art Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's Protection domain.

Claims (9)

  1. A kind of 1. Cu3SbS3Base thermoelectricity material, it is characterised in that it has cubic crystal structure, chemical general formula Cu3Sb1-xAxS3, Wherein A is cobalt and/or nickel, and x is 0.025~0.200.
  2. 2. Cu according to claim 13SbS3Base thermoelectricity material, it is characterised in that its sintering bulk density is not less than 4.85g/cm3, thermoelectricity capability index ZT is in 550~620K warm areas maximum not less than 0.55.
  3. 3. Cu according to claim 13SbS3Base thermoelectricity material, it is characterised in that the Cu3SbS3Base thermoelectricity material chemistry Form as Cu3Sb0.90Co0.10S3When, density 4.90g/cm3, thermoelectricity capability index ZT reaches in 550~620K warm area maximums 0.65；The Cu3SbS3Base thermoelectricity material chemical composition is Cu3Sb0.90Ni0.10S3When, density 4.93g/cm3, thermoelectricity capability Index ZT is in 550~620K warm areas maximum up to 0.62.
  4. A kind of 4. Emission in Cubic Cu3SbS3The preparation method of base thermoelectricity material, its feature mainly include the following steps that：
    1) dispensing：According to Cu3Sb1-xAxS3The mol ratio of each element in chemical general formula, weigh required elemental copper, antimony, A, sulphur and make For reaction raw materials, i.e., copper, antimony, A, the mol ratio of element sulphur are 3:(1-x):x:3, or slightly about fluctuated in this mol ratio, ripple Dynamic amplitude is less than 2%, and wherein A is cobalt and/or nickel, and x is 0.025~0.200；
    2) by after the step 1) reaction raw materials under inert gas atmosphere high-energy ball milling, using discharge plasma sintering or hot pressing Sintering process is densified, and obtains the Emission in Cubic Cu of high-performance, high-density3SbS3Base thermoelectricity material block.
  5. A kind of 5. Emission in Cubic Cu according to claim 43SbS3The preparation method of base thermoelectricity material, it is characterised in that step 2) the high-energy ball milling rotating speed described in is 350~650rpm, and the time is 15~30h, and ratio of grinding media to material is 10~30.
  6. A kind of 6. Emission in Cubic Cu according to claim 43SbS3The preparation method of base thermoelectricity material, it is characterised in that described The condition of discharge plasma sintering be：Under vacuum or inert atmosphere, sintering pressure is not less than 20MPa, and sintering temperature is 350~ 520 DEG C, sintering time is 1~30min.
  7. A kind of 7. Emission in Cubic Cu according to claim 43SbS3The preparation method of base thermoelectricity material, it is characterised in that described The condition of hot pressed sintering be：Under vacuum or inert atmosphere, sintering pressure is not less than 20MPa, and sintering temperature is 370~540 DEG C, Sintering time is 10~120min.
  8. A kind of 8. Emission in Cubic Cu according to claim 43SbS3The preparation method of base thermoelectricity material, it is characterised in that step 1) the ratio between amount of material of the copper, antimony, A, sulphur is 3:(1-x):x:3, wherein x are 0.05~0.1.
  9. A kind of 9. Emission in Cubic Cu according to claim 43SbS3The preparation method of base thermoelectricity material, it is characterised in that step 1) copper, antimony, sulphur, cobalt, nickel, purity described in are not less than 99%, are elemental powders.
CN201710519492.9A 2017-06-30 2017-06-30 Cubic phase Cu 3 SbS 3 -based thermoelectric material and method for preparing thermoelectric material through element replacement Expired - Fee Related CN107359232B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111162160A (en) * 2018-11-08 2020-05-15 中国科学院大连化学物理研究所 P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof
CN111883640A (en) * 2020-07-30 2020-11-03 河南理工大学 Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
胡赓祥，蔡珣: "《材料科学基础》", 31 December 2000 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111162160A (en) * 2018-11-08 2020-05-15 中国科学院大连化学物理研究所 P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof
CN111162160B (en) * 2018-11-08 2023-09-26 中国科学院大连化学物理研究所 P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof
CN111883640A (en) * 2020-07-30 2020-11-03 河南理工大学 Cubic phase Cu3SbS3Base thermoelectric material and preparation method thereof

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