CN108821771A - A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material - Google Patents

A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material Download PDF

Info

Publication number
CN108821771A
CN108821771A CN201810534585.3A CN201810534585A CN108821771A CN 108821771 A CN108821771 A CN 108821771A CN 201810534585 A CN201810534585 A CN 201810534585A CN 108821771 A CN108821771 A CN 108821771A
Authority
CN
China
Prior art keywords
powder
silver
thermoelectricity capability
ternary compound
mse
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810534585.3A
Other languages
Chinese (zh)
Other versions
CN108821771B (en
Inventor
刘呈燕
王秀霞
苗蕾
伍少海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guilin University of Electronic Technology
Original Assignee
Guilin University of Electronic Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guilin University of Electronic Technology filed Critical Guilin University of Electronic Technology
Priority to CN201810534585.3A priority Critical patent/CN108821771B/en
Publication of CN108821771A publication Critical patent/CN108821771A/en
Application granted granted Critical
Publication of CN108821771B publication Critical patent/CN108821771B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Composite Materials (AREA)
  • Thermal Sciences (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of preparation methods of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material, synthesize Ag using hydro-thermal reaction methodxMSey(M is selected from any one of Sn, Cr, Bi, Ga and Al) black nano powder, further it is heat-treated in atmosphere tube type furnace, again by adulterating halogen atom under high temperature after quartz ampoule vacuum sealing tube, optimize its thermoelectricity capability, the Ag with high thermoelectricity capability is made using hot-pressing sintering techniquexMSeyPolycrystalline bulk material, this method synthesis technology is simple, and raw materials are resourceful, and product purity is higher, and it is the thermoelectric material with high thermoelectricity capability that sample high temperature performance, which is stablized,.

Description

A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material
Technical field：
The present invention relates to thermoelectric material science and technology fields, and in particular to a kind of high thermoelectricity capability silver selenium ternary compound is more The preparation method of crystal block body material.
Background technique：
The world today, demand of the whole world to substitution clean energy resource have greatly pushed the rapid hair of thermoelectricity (TE) investigation of materials Exhibition, it can realize that waste heat is collected by the application thermal gradient direct generation of electricity.Silver-colored selenium ternary compound crystalline material is a kind of public Excellent thermoelectricity (TE) material recognized, this kind of unique bonding feature of compound cause it with structure abundant, weaker chemistry Key causes it to can be insulator, semiconductor, electronic conductor even according to its structure, the difference of composition with the lower velocity of sound It is superconductor, it is many-sided with important purposes in light, electricity, magnetic etc..The transfer efficiency of TE device by material Carnot efficiency and Dimensionless performance ZT=[S2σT/(ke+kl)] limitation, wherein S is Seebeck coefficient, and σ is conductivity, keIt is electronics thermal conductivity Rate, klLattice thermal conductivity, T are absolute temperature.High zt needs high Seebeck coefficient, the combination of high conductivity and low heat conductivity. But all these parameters all interdepend, it is interactional, therefore be difficult to synchronize and get a promotion.Current research tendency It is to find the thermoelectric material with lower intrinsic thermal conductivity, then optimizes power factor on this basis, reaches acquisition compared with high fever The purpose of electrical property.At high temperature, thermal conductivity is lower than the glass limit, thermal capacitance C to this kind of silver selenium ternary compoundsVLower than 3NkB, Wherein N is Avogadro's number, kBIt is Boltzmann constant, embodies good Seebeck coefficient (N-shaped) and conductivity, because This is a kind of promising warm thermoelectric material.So far, the typical method for preparing silver-colored selenium ternary compound both at home and abroad is main Include the following three types flux growth metrhod, solid-phase synthesis, solvent-thermal method.
Summary of the invention：
The purpose of the invention is to provide a kind of system of the silver-colored selenium ternary compound polycrystalline bulk material of high thermoelectricity capability Preparation Method, using the synthetic method of hydro-thermal reaction growth crystal, reaction raw materials incrementally react synthesis target product, by changing Become reaction temperature and the reaction time in depth realizes Effective Regulation on size, pattern, composition and phase structure to it, then leads to It crosses and predecessor is further heat-treated, introduce heteroatom, replace Se, regulate and control defect, improve carrier concentration, thus Conductivity is improved, thermoelectric figure of merit ZT is advanced optimized, enhances its mechanical performance using hot-pressing sintering technique, so that densification be made Degree is high, mechanical strength is good, lower thermal conductivity silver-colored selenium ternary compound polycrystalline bulk material, and synthesis temperature is low, in preparation process In without using surfactant and organic additive, energy conservation and environmental protection is at low cost.
The present invention is achieved by the following technical programs：
A kind of high thermoelectricity capability chemical formula is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk material preparation method, It is characterized in that, M is selected from any one of Sn, Cr, Bi, Ga and Al, and x, y are positive integer；When M is Sn, x=8, y=6；M is Cr When with Bi, x=1, y=2；When X is Ga and Al, x=9, y=6；This approach includes the following steps：
(1) Ag is pressedxMSeyThe corresponding molar ratio of each element is by the predecessor AgNO of Ag in chemical formula3, Se predecessor SeO2, M predecessor containing M chlorate composition solid material be added reaction vessel polytetrafluoroethyllining lining in, and be added go Ionized water, every 50ml deionized water match 2.2505-11.2525g solid material, and reducing agent N is added after stirring2H4·H2O, often 2.2505g solid material matches 1-8ml reducing agent N2H4·H2O continues stirring and is sufficiently mixed, polytetrafluoroethyllining lining is put on Stainless steel autoclave, and seal, it is then heated to 120-200 DEG C, is reacted 6~24 hours；It is cooled to room after reaction Temperature, obtained sediment nano-powder filter wash with distilled water, are then not less than 1 hour with soaked in absolute ethyl alcohol, true Dry 12-24h obtains silver-colored selenium ternary compound nano-powder at 60-80 DEG C in empty drying box；
(2) the silver-colored selenium ternary compound nano-powder that step (1) obtains be cold-pressed into after block in atmosphere tube type furnace in It is heat-treated 2-16 hours at 400-800 DEG C, wherein the pressure being cold-pressed is not less than 318 kilograms/square centimeter, atmosphere tube type furnace institute It is the gaseous mixture of argon gas and hydrogen with atmosphere, volume ratio shared by hydrogen is 1%-8%, and heat treatment gained block is ground at powder Selected solid material is adulterated with halogen atom afterwards to mix, then is packaged in vitreosil pipe by quartz ampoule encapsulation technology, later 500 to 700 DEG C of progress halogen atom doping are heated to, the dosage that halogen atom adulterates selected solid material presses nHalogen atom/ (nHalogen atom+nSe) value be 1% to 4% to calculate, the halogen atom is selected from Cl or Br, then in hot pressing furnace, 300 to 600 DEG C At a temperature of be sintered within hot pressing 30-360 minutes, wherein pressure be 30-50MPa, it is ternary finally to obtain high thermoelectricity capability silver selenium Close object AgxMSeyPolycrystalline bulk material.
When M is selected from Sn, the stanniferous chlorate of the predecessor of Sn is selected from SnCl in step (1)2·2H2O、SnCl2、SnCl4· 5H2Any one in O, the selected raw material of halogen atom Cl or Br doping respectively corresponds as SnCl in step (2)2Or SnBr2。
When M is selected from Cr, the predecessor of M is CrCl in step (1)3·6H2O, in step (2) selected by halogen atom Cl doping Raw material is CrCl3。
When M is selected from Bi, the predecessor of M is BiCl in step (1)3；In step (2) selected by halogen atom Cl or Br doping Raw material respectively correspond as BiCl3Or BiBr3。
When M is selected from Ga, the predecessor of M is GaCl in step (1)3；In step (2) selected by halogen atom Cl or Br doping Raw material respectively correspond as GaCl3Or GaBr3。
When M is selected from Al, the predecessor of M is AlCl in step (1)3；In step (2) selected by halogen atom Cl or Br doping Raw material respectively correspond as AlCl3Or AlBr3。
Preferably, step (2) heat treatment is raised to 600-800 DEG C with the heating rate not less than 5 DEG C/min.
Step (2) can be at 0.01L/min between 1L/min by the airflow rate of sample.
It is of the invention compared with the prior art, having the advantage that：
1) present invention is innovatively using the synthetic method of hydro-thermal reaction growth crystal, in a closed system, Under the spontaneous pressure of certain temperature and solvent, reaction raw materials incrementally react synthesis target product, by changing reaction temperature Degree and reaction time in depth realize Effective Regulation on size, pattern, composition and phase structure to it, then by forerunner Object is further heat-treated, and heteroatom is introduced, and replaces Se, regulates and controls defect, carrier concentration is improved, to improve conductance Rate advanced optimizes thermoelectric figure of merit ZT, enhances its mechanical performance using hot-pressing sintering technique, so that consistency height, machine be made Tool intensity is good, the silver-colored selenium ternary compound polycrystalline bulk material of the high thermoelectricity capability of lower thermal conductivity, high power factor.
2) synthesis technology of the present invention is simple, and raw material resources are abundant, and synthesis temperature is low, does not use during the preparation process Surfactant and organic additive, the silver-colored selenium ternary compound polycrystalline Nano material surface cleaning after deionized water is cleaned, energy Its due function is played to the greatest extent, and energy conservation and environmental protection is at low cost, and product high temperature performance is stablized, and has high power factor And lower thermal conductivity.
Detailed description of the invention：
Fig. 1 is the Ag of 1 hydro-thermal reaction method of embodiment of the present invention synthesis8SnSe6The X-ray diffraction picture of nano-powder；
Fig. 2 is the Ag of 1 hydro-thermal reaction method of embodiment of the present invention synthesis8SnSe6The resistivity of polycrystalline Nano block, Seebeck Coefficient, power factor variation with temperature curve graph variation with temperature curve graph.
Specific embodiment：
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1：
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.4513g SnCl in chemical formula2·2H2O、 2.7179gAgNO3With 1.3315g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total It measures as 4.5007 g), and 50ml deionized water is added in the reaction vessel.Measure 6ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 150 DEG C, 6h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then every It is secondary to be washed the resulting hydro-thermal reaction sediment of above-mentioned steps with 500ml deionized water, in triplicate, then filter.With anhydrous 80 DEG C of vacuum drying 12h are after ethyl alcohol impregnates 1 hour to get Ag8SnSe6Black nano powder, XRD are as shown in Figure 1. Ag8SnSe6Nano-powder is heat-treated 16h after being cold-pressed into block in atmosphere tube type furnace, and heat treatment temperature is 400 DEG C, wherein being cold-pressed Pressure be 318 kilograms/square centimeter, atmosphere used in atmosphere tube type furnace is the gaseous mixture of argon gas and hydrogen, body shared by hydrogen Product than be 1%, heat treatment gained block it is ground at after powder with SnCl2Solid material presses nCl/(nCl+nSe) value be 3% Proportion mixing, then be packaged in vitreosil pipe by quartz ampoule encapsulation technology, it is heated to 500 DEG C of progress halogen atoms later Cl doping, then be sintered at 600 DEG C in hot pressing furnace 30 minutes, wherein pressure is 30MPa.It is high (relatively close to obtain consistency 98%) and high thermoelectricity capability Ag degree is8SnSe6Polycrystalline bulk material, resistivity, Seebeck coefficient and power factor such as Fig. 2 institute Show.
Embodiment 2
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.3792g SnCl in chemical formula2、2.7179gAgNO3With 1.3315 g SeO2(SnCl in polytetrafluoroethyllining lining is added2、AgNO3And SeO2The total amount of powder is 4.4286g), and be added 50ml deionized water is in the reaction vessel.Measure 6ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring ten Minute, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 120 DEG C is heated to, is reacted under constant temperature 6h pours into resulting nano-powder in beaker to its cooled to room temperature, stands.Then 500ml deionized water is used every time By the resulting hydro-thermal reaction sediment washing of above-mentioned steps, in triplicate, then filter.With after soaked in absolute ethyl alcohol 1 hour 80 DEG C vacuum drying 12h to get Ag8SnSe6Black nano powder.Ag8SnSe6Nano-powder is cold-pressed into after block in atmosphere tube type 2h is heat-treated in furnace, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is 318 kilograms/square centimeter, atmosphere tube type furnace Atmosphere used is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, heat treatment gained block it is ground at powder after With SnBr2Solid material presses nBr/(nBr+nSe) value be 1% proportion mix, then be packaged in very by quartz ampoule encapsulation technology In empty quartz ampoule, it is heated to 700 DEG C of progress halogen atom Br doping later and is sintered 30 minutes at 500 DEG C in hot pressing furnace again, Wherein pressure is 40MPa.Obtain thermoelectricity capability and the comparable Ag of embodiment one8SnSe6Polycrystalline bulk material.
Embodiment 3
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.7012g SnCl in chemical formula4·5H2O、 2.7179gAgNO3With 1.3315g SeO2(SnCl in polytetrafluoroethyllining lining is added4·5H2O、AgNO3And SeO2Powder it is total Amount is 4.7506g), and 50ml deionized water is added in the reaction vessel.Measure 6ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 150 DEG C, 6h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then every It is secondary to be washed the resulting hydro-thermal reaction sediment of above-mentioned steps with 500ml deionized water, in triplicate, then filter.With anhydrous 60 DEG C of vacuum drying are for 24 hours to get Ag after ethyl alcohol impregnates 4 hours8SnSe6Black nano powder.Ag8SnSe6Nano-powder is cold-pressed into Be heat-treated 2h after block in atmosphere tube type furnace, heat treatment temperature is 800 DEG C, wherein the pressure being cold-pressed be 350 kilograms/square Centimetre, atmosphere used in atmosphere tube type furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, heat treatment gained block Body it is ground at after powder with SnCl2Solid material presses nCl/(nCl+nSe) value be 4% proportion mix, then pass through quartz ampoule Encapsulation technology is packaged in vitreosil pipe, is heated to 600 DEG C of progress halogen atom Cl doping later, then in hot pressing furnace in It is sintered at 600 DEG C 30 minutes, wherein pressure is 30MPa.Obtain thermoelectricity capability and the comparable Ag of embodiment one8SnSe6Polycrystalline Block materials.
Embodiment 4
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.9026g SnCl in chemical formula2·2H2O、 5.4358gAgNO3With 2.6630g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total Amount is 9.0014g), and 50ml deionized water is added in the reaction vessel.Measure 4ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 200 DEG C, 6h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then every It is secondary to be washed the resulting hydro-thermal reaction sediment of above-mentioned steps with 500ml deionized water, in triplicate, then filter.With anhydrous In 80 DEG C of vacuum drying 12h to get Ag after ethyl alcohol immersion 2 hours8SnSe6Black nano powder.Ag8SnSe6Nano-powder cold pressing At 2h is heat-treated after block in atmosphere tube type furnace, heat treatment temperature is 800 DEG C, wherein the pressure being cold-pressed is 318 kilograms/flat Square centimetre, atmosphere used in atmosphere tube type furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, heat treatment gained Block it is ground at after powder with SnCl2Solid material presses nCl/(nCl+nSe) value be 1% proportion mix, then pass through quartz Pipe encapsulation technology is packaged in vitreosil pipe, is heated to 500 DEG C of progress halogen atom Cl doping later, then in hot pressing furnace It is sintered at 300 DEG C 360 minutes, wherein pressure is 40MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one8SnSe6Polycrystalline Block materials.
Embodiment 5
By AgBiSe2The corresponding molar ratio of each element weighs 3.1535gBiCl in chemical formula3、3.3974gAgNO3With 2.2192g SeO2(BiCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 8.7701g), and be added 50ml deionized water is in the reaction vessel.Measure 6ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring ten Minute, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 200 DEG C is heated to, is reacted under constant temperature 6h pours into resulting nano-powder in beaker to its cooled to room temperature, stands.Then 500ml deionized water is used every time By the resulting hydro-thermal reaction sediment washing of above-mentioned steps, in triplicate, then filter.With after soaked in absolute ethyl alcohol 4 hours 80 DEG C of vacuum drying 12h are to get AgBiSe2Black nano powder.AgBiSe2Nano-powder is cold-pressed into after block in atmosphere tube type 16h is heat-treated in furnace, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is 320 kilograms/square centimeter, atmosphere tube type furnace Atmosphere used is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, heat treatment gained block it is ground at powder after With BiCl3Solid material presses nCl/(nCl+nSe) value be 3% proportion mix, then be packaged in very by quartz ampoule encapsulation technology In empty quartz ampoule, it is heated to 500 DEG C of progress halogen atom Cl doping later, then is sintered 360 points at 300 DEG C in hot pressing furnace Clock, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable AgBiSe of embodiment one2Polycrystalline bulk material.
Embodiment 6
By AgBiSe2The corresponding molar ratio of each element weighs 3.1535gBiCl in chemical formula3、3.3974gAgNO3With 2.2192g SeO2(BiCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 8.7701g), and be added 50ml deionized water is in the reaction vessel.Measure 6ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring ten Minute, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 200 DEG C is heated to, is reacted under constant temperature For 24 hours, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then 500ml deionization is used every time Water washs the resulting hydro-thermal reaction sediment of above-mentioned steps, in triplicate, then filters.After soaked in absolute ethyl alcohol 4 hours In 80 DEG C of vacuum drying 12h to get AgBiSe2Black nano powder.AgBiSe2Nano-powder is cold-pressed into after block in atmosphere pipe 16h is heat-treated in formula furnace, heat treatment temperature is 700 DEG C, wherein the pressure being cold-pressed is 320 kilograms/square centimeter, atmosphere tube type Atmosphere used in furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, and heat treatment gained block is ground at powder Afterwards with BiBr3Solid material presses nBr/(nBr+nSe) value be 4% proportion mix, then be packaged in by quartz ampoule encapsulation technology In vitreosil pipe, it is heated to 600 DEG C of progress halogen atom Br doping later, then is sintered 360 points at 300 DEG C in hot pressing furnace Clock, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable AgBiSe of embodiment one2Polycrystalline bulk material.
Embodiment 7
By Ag9GaSe6The corresponding molar ratio of each element weighs 0.3521gGaCl in chemical formula3、3.0577gAgNO3With 1.3315g SeO2(GaCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 4.7413g), and be added 50ml deionized water is in the reaction vessel.Measure 16ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring Ten minutes, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 150 DEG C is heated to, is reacted under constant temperature 18h pours into resulting nano-powder in beaker to its cooled to room temperature, stands.Then 500ml deionization is used every time Water washs the resulting hydro-thermal reaction sediment of above-mentioned steps, in triplicate, then filters.After soaked in absolute ethyl alcohol 1 hour In 80 DEG C of vacuum drying 2h to get Ag9GaSe6Black nano powder.Ag9GaSe6Nano-powder is cold-pressed into after block in atmosphere pipe 12h is heat-treated in formula furnace, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is 318 kilograms/square centimeter, atmosphere tube type Atmosphere used in furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, and heat treatment gained block is ground at powder Afterwards with GaCl3Solid material presses nCl/(nCl+nSe) value be 4% proportion mix, mixing sealed again by quartz ampoule encapsulation technology It is sintered at 600 DEG C loaded in vitreosil pipe, being heated to 700 DEG C of progress halogen atom Cl doping later, then in hot pressing furnace 30 minutes, wherein pressure was 50MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one9GaSe6Polycrystalline bulk material.
Embodiment 8
By Ag9GaSe6The corresponding molar ratio of each element weighs 0.3521gGaCl in chemical formula3、3.0577gAgNO3With 1.3315g SeO2(GaCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 4.7413g), and be added 50ml deionized water is in the reaction vessel.Measure 16ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring Ten minutes, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 150 DEG C is heated to, is reacted under constant temperature 18h pours into resulting nano-powder in beaker to its cooled to room temperature, stands.Then 500ml deionization is used every time Water washs the resulting hydro-thermal reaction sediment of above-mentioned steps, in triplicate, then filters.After soaked in absolute ethyl alcohol 1 hour In 80 DEG C of vacuum drying 2h to get Ag9GaSe6Black nano powder.Ag9GaSe6Nano-powder is cold-pressed into after block in atmosphere pipe 12h is heat-treated in formula furnace, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is 318 kilograms/square centimeter, atmosphere tube type Atmosphere used in furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, and heat treatment gained block is ground at powder Afterwards with GaBr3Solid material presses nBr/(nBr+nSe) value be 1% proportion mix, mixing sealed again by quartz ampoule encapsulation technology It is sintered at 400 DEG C loaded in vitreosil pipe, being heated to 700 DEG C of progress halogen atom Br doping later, then in hot pressing furnace 30 minutes, wherein pressure was 50MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one9GaSe6Polycrystalline bulk material.
Embodiment 9
By Ag9AlSe6The corresponding molar ratio of each element weighs 0.2667gAlCl in chemical formula3、5.0961gAgNO3With 2.2192g SeO2(AlCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 7.582g), and be added 50ml deionized water is in the reaction vessel.Measure 10ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring Ten minutes, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 120 DEG C is heated to, is reacted under constant temperature For 24 hours, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then 500ml deionization is used every time Water washs the resulting hydro-thermal reaction sediment of above-mentioned steps, in triplicate, then filters.After soaked in absolute ethyl alcohol 2 hours In 80 DEG C of vacuum drying 12h to get Ag9AlSe6Black nano powder.Ag9AlSe6Nano-powder is cold-pressed into after block in atmosphere 12h is heat-treated in tube furnace, heat treatment temperature is 600 DEG C, wherein the pressure being cold-pressed is 400 kilograms/square centimeter, atmosphere pipe Atmosphere used in formula furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, and heat treatment gained block is ground at powder Last and AlCl3Solid material presses nCl/(nCl+nSe) value be 1% proportion mix, mixing again pass through quartz ampoule encapsulation technology It is packaged in vitreosil pipe, is heated to 500 DEG C of progress halogen atom Cl doping later, then be sintered at 500 DEG C in hot pressing furnace 60 minutes, wherein pressure was 30MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one9AlSe6Polycrystalline bulk material.
Embodiment 10
By Ag9AlSe6The corresponding molar ratio of each element weighs 0.2667gAlCl in chemical formula3、5.0961gAgNO3With 2.2192g SeO2(AlCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 7.582g), and be added 50ml deionized water is in the reaction vessel.Measure 10ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring Ten minutes, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 120 DEG C is heated to, is reacted under constant temperature For 24 hours, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then 500ml deionization is used every time Water washs the resulting hydro-thermal reaction sediment of above-mentioned steps, in triplicate, then filters.After soaked in absolute ethyl alcohol 2 hours In 80 DEG C of vacuum drying 12h to get Ag9AlSe6Black nano powder.Ag9AlSe6Nano-powder is cold-pressed into after block in atmosphere 12h is heat-treated in tube furnace, heat treatment temperature is 600 DEG C, wherein the pressure being cold-pressed is 400 kilograms/square centimeter, atmosphere pipe Atmosphere used in formula furnace is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, and heat treatment gained block is ground at powder Last and AlBr3Solid material presses nBr/(nBr+nSe) value be 4% proportion mix, mixing again pass through quartz ampoule encapsulation technology It is packaged in vitreosil pipe, is heated to 500 DEG C of progress halogen atom Br doping later, then be sintered at 600 DEG C in hot pressing furnace 60 minutes, wherein pressure was 50MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one9AlSe6Polycrystalline bulk material.
Embodiment 11
By AgCrSe2The corresponding molar ratio of each element weighs 3.167g CrCl in chemical formula3、3.3974gAgNO3With 4.4384g SeO2(CrCl in polytetrafluoroethyllining lining is added3、AgNO3And SeO2The total amount of powder is 11.0028g), and be added 50ml deionized water is in the reaction vessel.Measure 20ml N2H4·H2O is slowly added into polytetrafluoroethyllining lining, stirring Ten minutes, it is sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel autoclave, and close Envelope.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, 150 DEG C is heated to, is reacted under constant temperature 6h pours into resulting nano-powder in beaker to its cooled to room temperature, stands.Then 500ml deionized water is used every time By the resulting hydro-thermal reaction sediment washing of above-mentioned steps, in triplicate, then filter.With after soaked in absolute ethyl alcohol 1 hour 80 DEG C of vacuum drying 12h are to get AgCrSe2Black nano powder.AgCrSe2Nano-powder is cold-pressed into after block in atmosphere tube type 12h is heat-treated in furnace, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is 318 kilograms/square centimeter, atmosphere tube type furnace Atmosphere used is the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%-8%, and heat treatment gained block is ground at powder Last and CrCl3Solid material presses nCl/(nCl+nSe) value be 1% proportion mix, then encapsulated by quartz ampoule encapsulation technology In vitreosil pipe, it is heated to 600 DEG C of progress halogen atom Cl doping later, then is sintered 30 points at 600 DEG C in hot pressing furnace Clock, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable AgCrSe of embodiment one2Polycrystalline bulk material.
Embodiment 12
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.4513g SnCl in chemical formula2·2H2O、 2.7179gAgNO3With 1.3315g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total Amount is 4.5007g), and 50ml deionized water is added in the reaction vessel.Measure 10ml N2H4·H2O is slowly added into poly- In tetrafluoroethene liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on not Become rusty steel autoclave, and seals.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to , 6h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, stand by 150 DEG C.So The resulting hydro-thermal reaction sediment of above-mentioned steps is washed with 500ml deionized water every time afterwards, in triplicate, is then filtered.With In 80 DEG C of vacuum drying 12h to get Ag after soaked in absolute ethyl alcohol 1 hour8SnSe6Black nano powder.Ag8SnSe6Nano-powder 16h is heat-treated in atmosphere tube type furnace after being cold-pressed into block, heat treatment temperature is 600 DEG C, wherein the pressure being cold-pressed is 318 kilograms Power/square centimeter, atmosphere used in atmosphere tube type furnace are the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, heat treatment Gained block it is ground at after powder with SnCl2Solid material presses nCl/(nCl+nSe) value be 1% proportion mix, then pass through Quartz ampoule encapsulation technology is packaged in vitreosil pipe, is heated to 500 DEG C of progress halogen atom Cl doping later, then in hot pressing furnace In be sintered at 600 DEG C 30 minutes, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one8SnSe6It is more Crystal block body material.
Embodiment 13
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.4513g SnCl in chemical formula2·2H2O、 2.7179gAgNO3With 1.3315g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total Amount is 4.5007g), and 50ml deionized water is added in the reaction vessel.Measure 16ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 120 DEG C, 16h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then The resulting hydro-thermal reaction sediment of above-mentioned steps is washed with 500ml deionized water every time, in triplicate, is then filtered.With nothing In 60 DEG C of vacuum drying 12h to get Ag after water-ethanol immersion 2 hours8SnSe6Black nano powder.Ag8SnSe6Nano-powder 16h is heat-treated in atmosphere tube type furnace after being cold-pressed into block, heat treatment temperature is 600 DEG C, wherein the pressure being cold-pressed is 318 kilograms Power/square centimeter, atmosphere used in atmosphere tube type furnace are the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, heat treatment Gained block it is ground at after powder with SnCl2Solid material presses nCl/(nCl+nSe) value be 4% proportion mix, then pass through Quartz ampoule encapsulation technology is packaged in vitreosil pipe, is heated to 500 DEG C of progress halogen atom Cl doping later, then in hot pressing furnace In be sintered 30 minutes at 500 DEG C, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one8SnSe6It is more Crystal block body material.
Embodiment 14
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.4513g SnCl in chemical formula2·2H2O、 2.7179gAgNO3With 1.3315g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total Amount is 4.5007g), and 50ml deionized water is added in the reaction vessel.Measure 8ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 120 DEG C, it reacts under constant temperature for 24 hours, to its cooled to room temperature, resulting nano-powder is poured into beaker, stand.Then The resulting hydro-thermal reaction sediment of above-mentioned steps is washed with 500ml deionized water every time, in triplicate, is then filtered.With nothing In 80 DEG C of vacuum drying 14h to get Ag after water-ethanol immersion 5 hours8SnSe6Black nano powder.Ag8SnSe6Nano-powder 16h is heat-treated in atmosphere tube type furnace after being cold-pressed into block, heat treatment temperature is 800 DEG C, wherein the pressure being cold-pressed is 318 kilograms Power/square centimeter, atmosphere used in atmosphere tube type furnace are the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 8%, heat treatment Gained block it is ground at after powder with SnBr2Solid material presses nBr/(nBr+nSe) value be 1% proportion mix, then pass through Quartz ampoule encapsulation technology is packaged in vitreosil pipe, is heated to 700 DEG C of progress halogen atom Br doping later, then in hot pressing furnace In be sintered 90 minutes at 400 DEG C, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one8SnSe6It is more Crystal block body material.
Embodiment 15
By Ag8SnSe6The corresponding molar ratio of each element weighs 1.1285g SnCl in chemical formula2·2H2O、6.795gAgNO3 With 3.329g SeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2The total amount of powder is 11.2525g), and 50ml deionized water is added in the reaction vessel.Measure 40ml N2H4·H2O is slowly added into polytetrafluoro In ethylene liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining is put on into stainless steel Autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 150 DEG C, It reacts under constant temperature for 24 hours, to its cooled to room temperature, resulting nano-powder is poured into beaker, stand.Then every time The resulting hydro-thermal reaction sediment of above-mentioned steps is washed with 500ml deionized water, in triplicate, is then filtered.With anhydrous second Alcohol is dried in vacuo at 80 DEG C for 24 hours to get Ag after impregnating 1 hour8SnSe6Black nano powder.Ag8SnSe6Nano-powder is cold-pressed into Be heat-treated 2h after block in atmosphere tube type furnace, heat treatment temperature is 800 DEG C, gained block it is ground at after powder with SnCl2 Solid material presses nCl/(nCl+nSe) value be 4% proportion mix, then vitreosil pipe is packaged in by quartz ampoule encapsulation technology In, it is heated to 600 DEG C of progress halogen atom Cl doping later, then be sintered 60 minutes at 600 DEG C in hot pressing furnace, wherein pressure For 30 MPa, i.e. acquisition thermoelectricity capability and the comparable Ag of embodiment one8SnSe6Polycrystalline bulk material.
Embodiment 16
By Ag8SnSe6The corresponding molar ratio of each element weighs 0.2257g SnCl in chemical formula2·2H2O、 1.3590gAgNO3And 0.6658gSeO2(SnCl in polytetrafluoroethyllining lining is added2·2H2O、AgNO3And SeO2Powder it is total Amount is 2.2505g), and 50ml deionized water is added in the reaction vessel.Measure 1ml N2H4·H2O is slowly added into poly- four In vinyl fluoride liner, stirs ten minutes, be sufficiently mixed solution and reactant therein, polytetrafluoroethyllining lining put on stainless Steel autoclave, and seal.The reaction vessel of sealing obtained in above-mentioned steps is put into heating equipment, is heated to 150 DEG C, 6h is reacted under constant temperature, to its cooled to room temperature, resulting nano-powder is poured into beaker, is stood.Then every It is secondary to be washed the resulting hydro-thermal reaction sediment of above-mentioned steps with 500ml deionized water, in triplicate, then filter.With anhydrous In 80 DEG C of vacuum drying 12h to get Ag after ethyl alcohol immersion 2~4 hours8SnSe6Black nano powder.Ag8SnSe6Nano-powder 2h is heat-treated in atmosphere tube type furnace after being cold-pressed into block, heat treatment temperature is 400 DEG C, wherein the pressure being cold-pressed is not less than 318 Kilogram/square centimeter, atmosphere used in atmosphere tube type furnace are the gaseous mixture of argon gas and hydrogen, and volume ratio shared by hydrogen is 1%, heat Processing gained block it is ground at after powder with SnBr2Solid material presses nBr/(nBr+nSe) value be 3% proportion mix, mix Conjunction is packaged in vitreosil pipe by quartz ampoule encapsulation technology again, is heated to 500 DEG C of progress halogen atom Br doping later, then It is sintered at 600 DEG C in hot pressing furnace 30 minutes, wherein pressure is 30MPa, i.e. acquisition thermoelectricity capability and embodiment one is comparable Ag8SnSe6Polycrystalline bulk material.

Claims (8)

1. a kind of high thermoelectricity capability chemical formula is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk material preparation method, it is special Sign is that M is selected from any one of Sn, Cr, Bi, Ga and Al, and x, y are positive integer, when M is Sn, x=8, y=6；M is Cr and Bi When, x=1, y=2；When X is Ga and Al, x=9, y=6；This approach includes the following steps：
(1) Ag is pressedxMSeyThe corresponding molar ratio of each element is by the predecessor AgNO of Ag in chemical formula3, Se predecessor SeO2, M The solid material of chlorate composition of the predecessor containing M is added in reaction vessel polytetrafluoroethyllining lining, and deionized water is added, often 50ml deionized water matches 2.2505-11.2525g solid material, and reducing agent N is added after stirring2H4·H2O, every 2.2505g are solid Body raw material proportioning 1-8ml reducing agent N2H4·H2O continues stirring and is sufficiently mixed, polytetrafluoroethyllining lining is put on stainless steel high pressure Reaction kettle, and seal, it is then heated to 120-200 DEG C, is reacted 6~24 hours；It is cooled to room temperature after reaction, what is obtained is heavy Starch nano-powder filters wash with distilled water, then with soaked in absolute ethyl alcohol not less than 1 hour, in a vacuum drying oven Dry 12-24h obtains silver-colored selenium ternary compound nano-powder at 60-80 DEG C；
(2) the silver-colored selenium ternary compound nano-powder that step (1) obtains is cold-pressed into after block in atmosphere tube type furnace in 400-800 It is heat-treated 2-16 hours at DEG C, wherein the pressure being cold-pressed is not less than 318 kilograms/square centimeter, atmosphere used in atmosphere tube type furnace For the gaseous mixture of argon gas and hydrogen, volume ratio shared by hydrogen is 1%-8%, heat treatment gained block it is ground at after powder with halogen The atom doped selected solid material mixing of element, then be packaged in vitreosil pipe by quartz ampoule encapsulation technology, it is heated to later 500 to 700 DEG C of progress halogen atom doping, the dosage that halogen atom adulterates selected solid material press nHalogen atom/(nHalogen atom+nSe) Value calculates for 1% to 4%, and the halogen atom is selected from Cl or Br, then in 300 to 600 DEG C of at a temperature of hot pressing in hot pressing furnace It is sintered within 30-360 minutes, wherein pressure is 30-50MPa, finally obtains the silver-colored selenium ternary compound of high thermoelectricity capability AgxMSeyPolycrystalline bulk material.
2. high thermoelectricity capability chemical formula according to claim 1 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk material Preparation method, which is characterized in that when M is selected from Sn, the stanniferous chlorate of the predecessor of Sn is selected from SnCl in step (1)2· 2H2O、SnCl2、SnCl4·5H2Any one in O, the selected raw material difference of halogen atom Cl or Br doping in step (2) Correspond to SnCl2Or SnBr2。
3. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that when M is selected from Cr, the predecessor of M is CrCl in step (1)3·6H2O；In step (2) The selected raw material of halogen atom Cl doping is CrCl3。
4. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that when M is selected from Bi, the predecessor of M is BiCl in step (1)3；Halogen is former in step (2) The selected raw material of sub- Cl or Br doping respectively corresponds as BiCl3Or BiBr3。
5. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that when M is selected from Ga, the predecessor of M is GaCl in step (1)3, halogen is former in step (2) The selected raw material of sub- Cl or Br doping respectively corresponds as GaCl3Or GaBr3。
6. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that when M is selected from Al, the predecessor of M is AlCl in step (1)3, halogen is former in step (2) The selected raw material of sub- Cl or Br doping respectively corresponds as AlCl3Or AlBr3。
7. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that step (2) heat treatment is raised to 600-800 with the heating rate not less than 5 DEG C/min ℃。
8. high thermoelectricity capability chemical formula according to claim 1 or 2 is AgxMSeySilver-colored selenium ternary compound polycrystalline bulk The preparation method of material, which is characterized in that step (2) by the airflow rate of sample can be at 0.01L/min to 1L/min it Between.
CN201810534585.3A 2018-05-29 2018-05-29 Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance Active CN108821771B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810534585.3A CN108821771B (en) 2018-05-29 2018-05-29 Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810534585.3A CN108821771B (en) 2018-05-29 2018-05-29 Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance

Publications (2)

Publication Number Publication Date
CN108821771A true CN108821771A (en) 2018-11-16
CN108821771B CN108821771B (en) 2020-06-09

Family

ID=64146760

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810534585.3A Active CN108821771B (en) 2018-05-29 2018-05-29 Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance

Country Status (1)

Country Link
CN (1) CN108821771B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603064A (en) * 2021-08-09 2021-11-05 深圳技术大学 Preparation method of silver bismuth selenium photo-thermal conversion nano material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130081444A (en) * 2012-01-09 2013-07-17 한국전기연구원 The manufacturing process of bi-te-se thermoelectric materials doped with silver
JP2015233055A (en) * 2014-06-09 2015-12-24 トヨタ自動車株式会社 Bismuth tellurium based nano composite thermoelectric material and method for manufacturing the same
CN105256161A (en) * 2015-11-04 2016-01-20 武汉理工大学 Unfired densification preparation process of Ag2Se block thermoelectric material
CN106098923A (en) * 2016-07-21 2016-11-09 同济大学 A kind of argyrodite thermoelectric material and preparation method thereof
CN107235477A (en) * 2017-07-04 2017-10-10 中国科学院上海硅酸盐研究所 A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130081444A (en) * 2012-01-09 2013-07-17 한국전기연구원 The manufacturing process of bi-te-se thermoelectric materials doped with silver
JP2015233055A (en) * 2014-06-09 2015-12-24 トヨタ自動車株式会社 Bismuth tellurium based nano composite thermoelectric material and method for manufacturing the same
CN105256161A (en) * 2015-11-04 2016-01-20 武汉理工大学 Unfired densification preparation process of Ag2Se block thermoelectric material
CN106098923A (en) * 2016-07-21 2016-11-09 同济大学 A kind of argyrodite thermoelectric material and preparation method thereof
CN107235477A (en) * 2017-07-04 2017-10-10 中国科学院上海硅酸盐研究所 A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李松浩等: "Ag掺杂SnSe化合物的制备及热电性能", 《无机材料学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603064A (en) * 2021-08-09 2021-11-05 深圳技术大学 Preparation method of silver bismuth selenium photo-thermal conversion nano material

Also Published As

Publication number Publication date
CN108821771B (en) 2020-06-09

Similar Documents

Publication Publication Date Title
CN104263986B (en) A kind of method of supper-fast preparation high-performance SnTe base thermoelectricity material
CN108588838B (en) method for preparing SnSe polycrystalline block with high thermoelectric performance
CN105671344B (en) One step prepares high-performance CoSb3The method of base thermoelectricity material
CN104934527B (en) A kind of Bi doped N-type Bi2S3The preparation method of thermoelectric material
CN111252802A (en) Silver-based chalcogenide Ag2Preparation method of X thermoelectric material
CN107400917A (en) A kind of SnSe2Crystalline compounds and its preparation method and application
CN111640853B (en) By Sb and Cu 2 Method for improving thermoelectric performance of n-type PbTe by Te co-doping
CN110078476A (en) A kind of Al doping BiCuSeO base thermoelectricity material and preparation method thereof
CN104810465B (en) Cu2-xS thermoelectric material preparation method
CN110408989B (en) Oxide thermoelectric material BiCuSeO monocrystal and preparation method thereof
CN108821771A (en) A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material
CN108598252A (en) Argyrodite type thermoelectric material and preparation method thereof
CN107689414B (en) Preparation method of multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases
CN106098922B (en) A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials
CN111048658A (en) SnI2Doped CsGeI3Perovskite thermoelectric material and preparation method thereof
CN103409656A (en) Thermoelectric material Mg2Sn and preparation method thereof
Goto et al. Effect of Bi Substitution on Thermoelectric Properties of SbSe2-based Layered Compounds NdO0. 8F0. 2Sb1− x Bi x Se2
CN104103750A (en) Preparation method of magnesium-silicon based silicon nanowire composite thermoelectric material
CN111883642B (en) Cu 2-x S-based thermoelectric material and solvothermal preparation method
CN107737921A (en) Thermoelectric material and preparation method thereof
CN101118946B (en) Barium zinc antimony based p type thermoelectric material and method for making same
CN105859299A (en) Na-doped cubic phase Ca2Si thermoelectric material and preparation method thereof
CN105600814A (en) Method for preparing Cu2O photoelectric material with flowerlike structure
CN105420528A (en) Method for preparing high-performance AgInTe2 thermoelectric material
CN109487106A (en) Quickly preparation Mg2(Si0.5Sn0.5)1-ySbyThe method of (0≤y≤0.025)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20181116

Assignee: Guangxi Liaofan Instrument Equipment Co.,Ltd.

Assignor: GUILIN University OF ELECTRONIC TECHNOLOGY

Contract record no.: X2022450000539

Denomination of invention: A Preparation Method of Silver Selenium Ternary Compound Polycrystalline Bulk Material with High Thermoelectric Properties

Granted publication date: 20200609

License type: Common License

Record date: 20221229