CN102766772B - Preparation method of Zn-Sb based thermoelectric material with secondary phase structure - Google Patents

Preparation method of Zn-Sb based thermoelectric material with secondary phase structure Download PDF

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CN102766772B
CN102766772B CN201110173100.0A CN201110173100A CN102766772B CN 102766772 B CN102766772 B CN 102766772B CN 201110173100 A CN201110173100 A CN 201110173100A CN 102766772 B CN102766772 B CN 102766772B
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崔教林
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Ningbo University of Technology
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Abstract

The invention relates to the field of new materials and is suitable for key component materials of moderate-temperature power generation for direct transition between heat energy and electric energy. The invention relates to a preparation method of a Zn-Sb based thermoelectric material with a secondary phase structure. A second component in the Zn-Sb based thermoelectric material is an intermetallic compound Cu5Zn3 containing a transition metal element Cu. According to the Zn-Sb based thermoelectric material, the intermetallic compound Cu5Zn3 is added according to the mol ratio of Zn4Sb3:Cu5Zn3=200:1 to obtain the thermoelectric material with its chemical formula being (Zn4Sb3)200(Cu5Zn3). The main point is to adopt spark plasma sintering (SPS) for the preparation. According to the thermoelectric material, 0.005 mol fraction of the intermetallic compound Cu5Zn3 is added into Zn4Sb3 so as to form the thermoelectric material with its chemical formula being (Zn4Sb3)200(Cu5Zn3). The thermoelectric material (Zn4Sb3)200(Cu5Zn3) is synthesized by powder metallurgy, and its preparation technology is carried out by five steps. The preparation method provided by the invention has advantages of simple technology and low cost. The material, which has environmental protection performance and has no pollution or noise, is a green energy material.

Description

The Zn-Sb base thermoelectricity material preparation method with secondary phase weave construction
Technical field
The present invention relates to be applicable to the directly key components material of the middle temperature generating of conversion of heat energy and electric energy, is a kind of Zn-Sb base thermoelectricity material preparation method with secondary phase weave construction.
Background technology
Thermoelectric material is a kind of by current carrier, comprises that the motion in electronics or hole realizes electric energy and the direct novel semi-conductor functional materials of conversion mutually of heat energy.The generating of being made by thermoelectric material and refrigeration plant have that volume is little, pollution-free, noiselessness, without advantages such as wearing and tearing, good reliability, life-span are long.In civil area, potential range of application as: home freezer, refrigerator, superconductive electronic device is cooling and cogeneration, used heat utilization power supply and side area small-scale power-plant device etc.
The over-all properties of thermoelectric material is by zero dimension thermoelectric figure of merit zT= tsa 2/ k,wherein abe Seebeck coefficient, sbe specific conductivity, kbe thermal conductivity, tabsolute temperature.Therefore, the performance of thermoelectric material and temperature have close relationship.Up to now, the homogeneous thermoelectric material of finding, its highest thermoelectric figure of merit ( zT) only under some temperature values, just obtain maximum value.At present, the middle temperature of having been applied is among a small circle mainly Pb-Te base and the metal silicide series alloy of fifties exploitation with thermoelectric power generation material, and the former its maximum thermoelectric figure of merit is in 1.5 left and right, but Pb environmental pollution is larger, and human body is also had to injury.The latter's thermoelectricity capability is lower, and its thermoelectric figure of merit is generally in 0.3 left and right, maximum thermoelectric figure of merit zT≤ 0.6.The preparation characteristic of metal antimonide Zn-Sb base thermoelectricity material is preparation technology's more complicated, and heat processing technique (especially temperature) is difficult to control.546 oduring C, can there is L(liquid phase)+d-Zn 4sb 3b-Zn 4sb 3peritectic Reaction; 493 oduring C, b can separate out g phase in inside mutually.Therefore, improper if temperature is controlled, be difficult to obtain the higher b-Zn of purity 4sb 3phase.While is due to volatilization or the disappearance of Zn element in material preparation process, at b-Zn 4sb 3base tends to crystallization in mutually and goes out ZnSb secondary phase.Generally this ZnSb secondary phase is to b-Zn 4sb 3the negative impact of base thermoelectricity capability is larger.If but can change ZnSb Xiang tissue topography, and make this pattern favourable to improving thermoelectricity capability, not only simplified the preparation technology of Zn-Sb base thermoelectricity material, also can improve the thermoelectricity capability of material simultaneously.
At Zn 4sb 3in binary alloy, doping is the comparatively common means of improving its tissue and performance.The object of doping is by the feature that transports of the inner current carrier of coordinating material and phonon on the one hand, improves thermoelectricity capability; Can supplement on the other hand the disappearance of Zn element, the content of minimizing ZnSb secondary phase.
By to different elements or compound doped rear Zn 4sb 3the thermal treatment of sill, the pattern of change ZnSb phase, obtains shape as the ZnSb secondary phase weave construction of tree root shape.
Material preparation method is very big to the property relationship of material.Due to Zn 4sb 3the inside atomic arrangement of sill is very complicated, so the lattice thermal conductivity of material is often very low.Conventionally in laboratory or enterprise adopt the preparations such as its graceful method of boolean, zone melting method more, but this preparation method's cost is higher, industrial scale is restricted.Therefore another feature of the present invention is accurate designing material composition, adopts conventional powder metallurgic method to prepare material, then designs thermal treatment process, obtains required ZnSb secondary phase pattern, thereby reduces preparation Zn 4sb 3the cost of sill, raising thermoelectricity capability.
Summary of the invention
The present invention is by the intermetallic compound Cu selecting containing transition element Cu 5zn 3as Zn 4sb 3doping agent, thermal treatment process is worked out in design, changes the pattern of ZnSb secondary phase, improves thermo-electric conversion performance.Goal of the invention Shi Xiang this area provides a kind of Zn-Sb base thermoelectricity material preparation method of secondary phase weave construction, makes technique of the present invention simple, makes high-quality Zn 4sb 3thermoelectric material and technology of preparing for temperature in base, make its have thermoelectric figure of merit ( zTthe middle temperature p-type thermoelectric material of)=0.84, this block Zn 4sb 3its preparation technology is simple for base thermoelectricity material.The object of the invention is to take following technical scheme to realize.
A Zn-Sb base thermoelectricity material preparation method for secondary phase weave construction, the second component in described Zn-Sb base thermoelectricity material is the intermetallic compound Cu containing transition metal Cu 5zn 3, in this Zn-Sb base thermoelectricity material with mol ratio Zn 4sb 3: Cu 5zn 3compound C u between the ratio doping metals of=200:1 5zn 3, its main points are to adopt plasma discharging spark sintering (SPS) preparation, described Zn-Sb base thermoelectricity material is at Zn 4sb 3the Cu that inner doping molar fraction is 0.005 5zn 3intermetallic compound, forms thermoelectric material, and its chemical formula is (Zn 4sb 3) 200(Cu 5zn 3).
Above-mentioned (Zn 4sb 3) 200(Cu 5zn 3) thermoelectric material adopts powder metallurgic method synthetic, its preparation technology divides five steps to carry out:
The first step: melting is synthetic.First in vitreosil pipe, Zn is synthesized in melting respectively 4sb 3and Cu 5zn 3alloy, the former melting synthesis temperature is 700～900 ℃, and the latter is 1000～1200 ℃, and generated time is 24 hours.
Second step: Slow cooling.Zn after melting is synthetic in vitreosil pipe 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace.
The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 200:1 4sb 3) 200(Cu 5zn 3) material, be again placed on melting in vitreosil pipe and synthesize.Melting synthesis temperature is 1000～1200 ℃, and generated time is 24 hours.By (Zn 4sb 3) 200(Cu 5zn 3) behind ingot casting slow cooling to 700～900 ℃ immediately at quenching-in water.
The 4th step: sintering.By ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering (SPS), makes block.Sintering temperature is 350～550 ℃, sintering pressure 30～50MPa, soaking time 3 ~ 8 minutes.If sintering temperature is preferentially 450 ℃, sintering pressure 40MPa, soaking time is 5 minutes.
The 5th step: the block materials after sintering is again encapsulated in Glass tubing and anneals 20～28 hours.Before annealing, in Glass tubing, put a little a small amount of Zn particles, to reduce Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.
The ZnSb secondary phase that white tree root shape pattern is germinated in the inside of described Zn-Sb base thermoelectricity material.
Advantage of the present invention: Cu 5zn 3molar fraction is 0.005 (Zn 4sb 3) 200(Cu 5zn 3) material, after above-mentioned thermal treatment, inside has obtained the secondary phase weave construction of white tree root shape pattern.When 631K is 358 ℃, the Seebeck coefficient of material a=168.0 (μ V/K), specific conductivity s=3.58 ' 10 4w -1 .m -1, thermal conductivity k=077 (W .k -1 .m -1), maximum thermoelectric figure of merit zT=0.84; This material adopts conventional powder metallurgic method preparation, and technique is simple, and cost is lower; Material has environmental protection character, pollution-free, and noiselessness is a kind of green energy resource material.
Accompanying drawing explanation
Fig. 1 is microstructure picture of the present invention, and the position of arrow indication is a small amount of ZnSb secondary phase of white tree root shape pattern.In figure, a is the Cu that doping molar fraction is 0.005 5zn 3(Zn 4sb 3) 200(Cu 5zn 3) block thermoelectric material anneals after 24 hours at 350～550 ℃, the heterogeneous microstructure picture of material internal, doped with Cu 5zn 3(Zn afterwards 4sb 3) 200(Cu 5zn 3) thermoelectric material inside germinates a small amount of ZnSb secondary phase that white tree root shape pattern.In figure, b is the energy spectrometer analysis figure of material internal two-phase structure, and the tissue that has confirmed white tree root shape pattern is ZnSb phase.
Fig. 2 is that material property of the present invention contrasts schematic diagram with other material property.Ordinate zou in figure is zero dimension thermoelectric figure of merit zT; X-coordinate is temperature t/K; And with different marks, indicate the relation of its Chemical Composition and embodiment.
Table one is the performance synopsis of the embodiment of the present invention:
Table one
Figure 38738DEST_PATH_IMAGE001
The embodiment 1 to embodiment 5 providing in table one is Zn 4sb 3the performance of base p-type thermoelectric material, its composition proportion is (Zn 4sb 3) 200(Cu 5zn 3) material and Zn 4sb 3(embodiment 1), (Zn 4sb 3) 100(Cu 5zn 3) (embodiment 3), (Zn 4sb 3) 50(Cu 5zn 3) (embodiment 4), (Zn 4sb 3) 25(Cu 5zn 3) (embodiment 5) material carries out Performance Ratio.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Doped with Cu not 5zn 3binary alloy Zn 4sb 3its Seebeck coefficient is from 56.0 (mV of near room temperature .k -1) 127.50 (mVs of monotone increasing during to 657K .k -1); Specific conductivity but declines with temperature is dull, from 9.14 ' 10 of near room temperature 4w -1 .m -1while dropping to 657K 5.18 ' 10 4w -1 .m -1; Total heat conductance is from 0.94 (WK -1m -1) change to 1.14 (WK -1m -1).Doped with Cu 5zn 3after, Zn 4sb 3the Seebeck coefficient of base alloy starts with Cu 5zn 3content rise, work as Cu 5zn 3molar fraction reaches at 0.005 o'clock and starts to decline.The variation of specific conductivity is just in time contrary with the variation of Seebeck coefficient, when molar fraction reach minimum value while reaching 0.005, then start to rise.The comprehensive electrical performance of material is at Cu 5zn 3molar fraction reaches at 0.005 o'clock and obtains maximum value.Total heat conductance is along with Cu 5zn 3increased content and increase.
Above these three factors of comprehensive Seebeck coefficient, specific conductivity and thermal conductivity, are summarised as Cu in material 5zn 3content have a preferentially span, at this preferentially in scope, Thermal Synthetic electrical property zTvalue obtains maximum.In the present invention, this Cu preferentially 5zn 3content is molar fraction 0.005.Reaching under the temperature 633K of this maximum figure of merit (Zn 4sb 3) 200(Cu 5zn 3) specific conductivity of material is 3.58 ' 10 4w -1m -1; Seebeck coefficient is 168.0 (mV .k -1), total heat conductance is 0.77 (WK -1m -1), zero dimension thermoelectric figure of merit is 0.84.
Embodiment 1:
According to chemical formula Zn 4sb 3weighing purity is greater than Zn and Sb two elements of 99.999wt.% and is placed in respectively in vitreosil pipe.Melting synthesis temperature is 700～900 ℃, and melting generated time is 24 hours.Between smelting period, every 1 hour, jolt pipe, guarantee that reaction evenly.Synthetic rear first Slow cooling to 600～650 ℃ in stove of melting, then at quenching-in water.Ingot casting after quenching is through pulverizing, ball milling, and Ball-milling Time is controlled at 5 hours, and the powder after ball milling is shaped through plasma discharging spark sintering.Sintering temperature is 550～650 ℃, and sintering pressure is 30～50MPa, soaking time 3～8 minutes.Block materials after sintering is annealed 20～28 hours in glass tube with vacuum, and annealing temperature is 350～550 ℃.Before annealing, in Glass tubing, put a little a small amount of Zn particles, to reduce Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.
Embodiment 2:
At Zn 4sb 3the intermetallic compound Cu that middle doping molar fraction is 0.005 5zn 3.The first step: first according to chemical formula Zn 4sb 3and Cu 5zn 3weighing purity is greater than Zn, Cu and the Sb element of 99.999wt.% and is placed in respectively in different vitreosil pipes.The former melting synthesis temperature is 700～900 ℃, and the latter is 1000～1200 ℃, and generated time is 24 hours.Second step: Slow cooling.Zn after melting is synthetic in vitreosil pipe 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace.The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 200:1 4sb 3) 200(Cu 5zn 3) material, be again placed on melting in vitreosil pipe and synthesize.Melting synthesis temperature is 1000～1200 ℃, and generated time is 24 hours.By (Zn 4sb 3) 200(Cu 5zn 3) behind ingot casting slow cooling to 700～900 ℃ immediately at quenching-in water.The 4th step: sintering.By ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering, makes block.Sintering temperature is 350～550 ℃, and sintering pressure is 30～50MPa, soaking time 3～8 minutes.Preferentially sintering temperature is 450 ℃, and sintering pressure is 40MPa, and soaking time is 5 minutes.The 5th step: the block materials after sintering is again encapsulated in glass tube with vacuum and anneals 20～28 hours.Before annealing, in Glass tubing, put a little a small amount of Zn particles, to reduce the Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.
Embodiment 3:
At Zn 4sb 3the intermetallic compound Cu that middle doping molar fraction is 0.01 5zn 3.The first step: first according to chemical formula Zn 4sb 3and Cu 5zn 3weighing purity is greater than Zn, Cu and the Sb element of 99.999wt.% and is placed in respectively in different vitreosil pipes.The former melting synthesis temperature is 700～900 ℃, and the latter is 1000～1200 ℃, and generated time is 24 hours.Second step: Slow cooling.Zn after melting is synthetic in vitreosil pipe 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace.The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 100:1 4sb 3) 100(Cu 5zn 3) compound, be again placed on melting in vitreosil pipe and synthesize.Melting synthesis temperature is 1000～1200 ℃, and generated time is 24 hours.By (Zn 4sb 3) 100(Cu 5zn 3) behind ingot casting slow cooling to 700～900 ℃ immediately at quenching-in water.The 4th step: sintering.By ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering, makes block.Sintering temperature is 350～550 ℃, and sintering pressure is 30～50MPa, soaking time 3 ~ 8 minutes.If sintering temperature is preferentially 450 ℃, sintering pressure is 40MPa, and soaking time is 5 minutes.The 5th step: the block materials after sintering is again encapsulated in Glass tubing and anneals 20～28 hours.During Annealing is put a little a small amount of Zn particles in glass tube with vacuum, to reduce Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.
Embodiment 4:
At Zn 4sb 3the intermetallic compound Cu that middle doping molar fraction is 0.02 5zn 3.The first step: first according to chemical formula Zn 4sb 3and Cu 5zn 3weighing purity is greater than Zn, Cu and the Sb element of 99.999wt.% and is placed in respectively in different vitreosil pipes.The former melting synthesis temperature is 700～900 ℃, and the latter is 1000～1200 ℃, and generated time is 24 hours.Second step: Slow cooling.Zn after melting is synthetic in vitreosil pipe 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace.The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 50:1 4sb 3) 50(Cu 5zn 3) 1compound, is again placed on melting in vitreosil pipe and synthesizes.Melting synthesis temperature is 1000～1200 ℃, and generated time is 24 hours.By (Zn 4sb 3) 50(Cu 5zn 3) behind ingot casting slow cooling to 700～900 ℃ immediately at quenching-in water.The 4th step: sintering.By ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering, makes block.Sintering temperature is 350～550 ℃, and sintering pressure is 30～50MPa, soaking time 3 ~ 8 minutes.Preferentially sintering temperature is 450 ℃, and sintering pressure is 40MPa, and soaking time is 5 minutes.The 5th step: the block materials after sintering is again encapsulated in glass tube with vacuum and anneals 20～28 hours.During Annealing is put a little a small amount of Zn particles in Glass tubing, to reduce Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.
Embodiment 5:
At Zn 4sb 3the intermetallic compound Cu that middle doping molar fraction is 0.04 5zn 3.The first step: first according to chemical formula Zn 4sb 3and Cu 5zn 3weighing purity is greater than Zn, Cu and the Sb element of 99.999wt.% and is placed in respectively in different vitreosil pipes.The former melting synthesis temperature is 700 ~ 900 ℃, and the latter is 1000 ~ 1200 ℃, and generated time is 24 hours.Second step: Slow cooling.Zn after melting is synthetic in vitreosil pipe 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace.The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 25:1 4sb 3) 25(Cu 5zn 3) compound, be again placed on melting in vitreosil pipe and synthesize.Melting synthesis temperature is 1000 ~ 1200 ℃, and generated time is 24 hours.By (Zn 4sb 3) 25(Cu 5zn 3) behind ingot casting slow cooling to 700 ~ 900 ℃ immediately at quenching-in water.The 4th step: sintering.By ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering, makes block.Sintering temperature is 350～550 ℃, and sintering pressure is 30～50MPa, soaking time 3 ~ 8 minutes.Preferentially sintering temperature is 450 ℃, and sintering pressure is 40MPa, and soaking time is 5 minutes.The 5th step: the block materials after sintering is again encapsulated in glass tube with vacuum and anneals 20～28 hours.During Annealing is put a little a small amount of Zn particles in Glass tubing, to reduce Zn volatilization in block.350～550 ℃ of annealing temperatures, preferentially annealing temperature is 450 ℃, soaking time 24 hours.

Claims (2)

1. a Zn-Sb base thermoelectricity material preparation method with secondary phase weave construction, the second component in described Zn-Sb base thermoelectricity material is the intermetallic compound Cu containing transition metal Cu 5zn 3, in this Zn-Sb base thermoelectricity material with mol ratio Zn 4sb 3: Cu 5zn 3compound C u between the ratio doping metals of=200:1 5zn 3, it is characterized in that adopting plasma discharging spark sintering preparation, described Zn-Sb base thermoelectricity material is at Zn 4sb 3the Cu that inner doping molar fraction is 0.005 5zn 3intermetallic compound, forms thermoelectric material, and its chemical formula is (Zn 4sb 3) 200(Cu 5zn 3); Described (Zn 4sb 3) 200(Cu 5zn 3) thermoelectric material adopts powder metallurgic method synthetic, its preparation technology divides five steps to carry out:
The first step: melting is synthetic, first in vitreosil pipe, Zn is synthesized in melting respectively 4sb 3and Cu 5zn 3alloy, the former melting synthesis temperature is 700～900 ℃, and the latter is 1000～1200 ℃, and generated time is 24 hours;
Second step: Slow cooling, the Zn after in vitreosil pipe, melting being synthesized 4sb 3and Cu 5zn 3alloy cools to room temperature with the furnace;
The 3rd step: according to Zn 4sb 3with Cu 5zn 3mol ratio proportioning (Zn for 200:1 4sb 3) 200(Cu 5zn 3) material, be again placed on melting in vitreosil pipe and synthesize; Melting synthesis temperature is 1000～1200 ℃, and generated time is 24 hours, by (Zn 4sb 3) 200(Cu 5zn 3) behind ingot casting slow cooling to 700～900 ℃ immediately at quenching-in water;
The 4th step: sintering, by ingot casting pulverizing, ball milling after quenching, the powder after ball milling is shaped through plasma discharging spark sintering (SPS), makes block; Sintering temperature is 350～550 ℃, sintering pressure 30～50MPa, soaking time 3～8 minutes;
The 5th step: the block materials after sintering is again encapsulated in Glass tubing and anneals 20～28 hours is put a little a small amount of Zn particles in Glass tubing before annealing, to reduce Zn volatilization in block, 350～550 ℃ of annealing temperatures.
2. the Zn-Sb base thermoelectricity material preparation method with secondary phase weave construction according to claim 1, is characterized in that the ZnSb secondary phase that white tree root shape pattern is germinated in the inside of described Zn-Sb base thermoelectricity material.
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