CN104328500A - Clathrate, preparation method and applications thereof - Google Patents

Clathrate, preparation method and applications thereof Download PDF

Info

Publication number
CN104328500A
CN104328500A CN201410424124.2A CN201410424124A CN104328500A CN 104328500 A CN104328500 A CN 104328500A CN 201410424124 A CN201410424124 A CN 201410424124A CN 104328500 A CN104328500 A CN 104328500A
Authority
CN
China
Prior art keywords
runge
kutta integration
crucible
fusing assistant
silica tube
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
CN201410424124.2A
Other languages
Chinese (zh)
Other versions
CN104328500B (en
Inventor
徐静涛
刘永福
秦海明
蒋俊
江浩川
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.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
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 Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201410424124.2A priority Critical patent/CN104328500B/en
Publication of CN104328500A publication Critical patent/CN104328500A/en
Application granted granted Critical
Publication of CN104328500B publication Critical patent/CN104328500B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C30B29/52—Alloys
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • 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
    • H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a clathrate having a chemical formula of Ba8CuxGe<46-x>, wherein x represents a mole coefficient. (0.5=<x=<6) The clathrate is a mono crystal and has a high thermoelectric merit figure. At the same time, the invention further provides a preparation method and applications of the clathrate. The provided preparation method utilizes a flux process to prepare the clathrate so as to obtain a monocrystalline clathrate with excellent thermoelectric properties. The obtained monocrystalline clathrate has the advantages of large size and evenly-distributed elements. Moreover, the repeatability of the provided preparation method is high, the preparation process is simple, and thus the preparation method can be applied to massive production.

Description

Runge-Kutta integration and its preparation method and application
Technical field
The present invention relates to thermoelectric material, particularly relate to a kind of Runge-Kutta integration and its preparation method and application.
Background technology
Thermoelectric material can realize the mutual conversion between heat energy and electric energy.The advantages such as the thermo-electric device made by thermoelectric material has noiseless, nothing is worn and torn, volume is little, have great importance for raising traditional energy utilization ratio.
The performance of thermoelectric material is determined by thermoelectric figure of merit (ZT value): ZT=S 2σ T/ κ, wherein, S is Seebeck coefficient, and σ is specific conductivity, and κ is thermal conductivity, and T is absolute temperature.As can be seen here, high ZT value be obtained, need material to have higher Seebeck coefficient, higher specific conductivity and lower thermal conductivity, but there is stronger dependency in these parameters, is difficult to coordinated regulation.The nineties in last century, G.Slack proposes " phonon glasses electron crystal " concept, and the thermoelectric material thought should have lower thermal conductivity as glass, equally has higher specific conductivity with time image crystal.
Runge-Kutta integration has the controlled adjustable advantage of carrier concentration, has good thermoelectric material potentiality.But the synthesis of current Runge-Kutta integration is carried out mainly with melting (electric arc furnace electric arc melting or induction furnace induction fusing) or the mode of solid state reaction, and the Runge-Kutta integration obtained is polycrystalline.Impurity in Polycrystalline, border are more, reduce the mobility of current carrier, cause the ZT value of material to be difficult to promote.
Summary of the invention
The invention provides a kind of Runge-Kutta integration had compared with high zt, and the preparation method and application of this Runge-Kutta integration.
For achieving the above object, the present invention adopts following technical scheme:
A kind of Runge-Kutta integration, the chemical formula of described Runge-Kutta integration is Ba 8cu xge 46-x, wherein, x is mole coefficient, and 0.5≤x≤6; And described Runge-Kutta integration is monocrystalline.
Wherein in an embodiment, described Runge-Kutta integration belongs to isometric system, and space group is
A preparation method for described Runge-Kutta integration, comprises the following steps:
S100: take the reaction raw materials containing Ba element, Cu element and Ge element according to the stoichiometric ratio of component each in described Runge-Kutta integration;
S200: the described reaction raw materials taken is put into crucible, and adds fusing assistant; Or the reaction raw materials taken described in first utilizing prepares polycrystalline presoma, more described polycrystalline presoma is put into crucible, and add fusing assistant;
S300: by the described crucible sealed after being vacuumized being added with fusing assistant;
S400: the crucible of described sealing is placed in High Temperature Furnaces Heating Apparatus, after being warming up to 900 DEG C ~ 1200 DEG C, insulation 12h ~ 72h, is then cooled to 250 DEG C ~ 700 DEG C, obtains the mixture of Runge-Kutta integration and fusing assistant;
S500: take out described crucible at 250 DEG C ~ 700 DEG C, described Runge-Kutta integration is separated with described fusing assistant;
S600: described crucible is cooled to room temperature, takes out described Runge-Kutta integration.
Wherein in an embodiment, in S200, the reaction raw materials taken described in utilization is prepared polycrystalline presoma and is comprised the following steps:
The described reaction raw materials taken is put into crucible, by described crucible sealed after being vacuumized, then puts into High Temperature Furnaces Heating Apparatus sinter 4h ~ 8h at 950 DEG C ~ 1050 DEG C, obtain polycrystalline presoma;
Or the described reaction raw materials taken is put into crucible, be placed in induction furnace or electric arc furnace, pass into rare gas element or reducing gas, at 950 DEG C ~ 1050 DEG C, melting 4 ~ 8 hours, obtains polycrystalline presoma.
Wherein in an embodiment, described reaction raw materials is the simple substance of Ba, Cu, Ge, or Ba 6ge 25the simple substance of compound and Cu and Ge.
Wherein in an embodiment, in S400, be warming up to 900 DEG C ~ 1200 DEG C with the speed of 5 DEG C/min ~ 10 DEG C/min;
250 DEG C ~ 700 DEG C are cooled to the speed of 0.2 DEG C/h ~ 5 DEG C/h; Or after being first cooled to 850 DEG C ~ 950 DEG C with the speed of 5 DEG C/h ~ 10 DEG C/h, then be cooled to 250 DEG C ~ 700 DEG C with the speed of 0.2 DEG C/h ~ 5 DEG C/h.
Wherein in an embodiment, described fusing assistant is Sn or In.
Wherein in an embodiment, in S200, the molar weight of the fusing assistant of described interpolation is (1 ~ 8) with the ratio of the molar weight of Ba element in the described reaction raw materials taken: 1.
Wherein in an embodiment, in S300, oxyhydrogen flame, oxy-acetylene flame, coal gas oxygen flame or argon plasma flame is adopted to seal described crucible.
A kind of described application of Runge-Kutta integration in Thermoelectric Generator or thermoelectric cooling device.
Beneficial effect of the present invention is as follows:
Runge-Kutta integration of the present invention is single crystal structure, and compared with traditional polycrystalline Ba-Cu-Ge base Runge-Kutta integration, the border in the Ba-Cu-Ge base Runge-Kutta integration of single crystal structure in foreign matter content and crystal is obviously reduced, thus improves the rate of migration of current carrier; Meanwhile, due to the lattice parameter of filling the size of atom in Runge-Kutta integration, quality directly affects material, therefore, the thermal conductivity impact of filling atom pairs material is comparatively large, and the present invention adopts Ba atom as filling atom, reduces the thermal conductivity of material; Because thermoelectric figure of merit is directly proportional to the rate of migration of current carrier, and be inversely proportional to thermal conductivity, therefore, Runge-Kutta integration of the present invention has higher thermoelectric figure of merit.
The preparation method of Runge-Kutta integration of the present invention, utilizes flux method to carry out the preparation of Runge-Kutta integration, can obtain the monocrystal material of thermoelectricity capability excellence, the monocrystalline size obtained is comparatively large, and Elemental redistribution is even, and this preparation method's repetition rate is high, preparation process is simple, can be used for large-scale production.
Runge-Kutta integration of the present invention is widely used in Thermoelectric Generator or thermoelectric cooling device.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction pattern of the Runge-Kutta integration that the embodiment of the present invention 2 obtains;
Fig. 2 is the single crystal diffraction collection of illustrative plates of the Runge-Kutta integration that the embodiment of the present invention 2 obtains;
Fig. 3 is the laue photograph figure of the Runge-Kutta integration that the embodiment of the present invention 2 obtains;
The thermoelectric figure of merit variation with temperature curve of the Runge-Kutta integration that Fig. 4 obtains for the embodiment of the present invention 3 and embodiment 6.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of Runge-Kutta integration, chemical formula is Ba 8cu xge 46-x, wherein, x is mole coefficient, and 0.5≤x≤6; And this Runge-Kutta integration is monocrystalline.
Above-mentioned Runge-Kutta integration belongs to isometric system, and space group is ge atom and Cu atom form basic cubic structure framework to provide good thermoelectricity capability by covalent linkage, and have in unit cell by Ge atom and Cu atomic building caged space, Ba atom is then filled in the caged space of Ge atom and Cu atomic building.
Compared with traditional polycrystalline Ba-Cu-Ge base Runge-Kutta integration, the border in the Ba-Cu-Ge base Runge-Kutta integration foreign matter content of single crystal structure and crystal is obviously reduced, thus improves the rate of migration of current carrier; Meanwhile, due to the lattice parameter of filling the size of atom in Runge-Kutta integration, quality directly affects material, therefore, the thermal conductivity impact of filling atom pairs material is comparatively large, and the present invention adopts Ba atom as filling atom, reduces the thermal conductivity of material; Because thermoelectric figure of merit is directly proportional to the rate of migration of current carrier, and be inversely proportional to thermal conductivity, therefore, Runge-Kutta integration of the present invention has higher thermoelectric figure of merit.
Runge-Kutta integration of the present invention is widely used in Thermoelectric Generator or thermoelectric cooling device.
Present invention also offers the preparation method of above-mentioned Runge-Kutta integration, utilize flux method to carry out the preparation of Runge-Kutta integration, the monocrystal material of thermoelectricity capability excellence can be obtained, the monocrystalline size obtained is comparatively large, and Elemental redistribution is even, and this preparation method's repetition rate is high, preparation process is simple, can be used for large-scale production.
As a kind of embodiment, preparation method of the present invention comprises the following steps:
S100: according to Ba 8cu xge 46-xin (0.5≤x≤6), the stoichiometric ratio of each component takes the reaction raw materials containing Ba element, Cu element and Ge element.
The reaction raw materials taken in this step can be the simple substance of Ba, Cu, Ge, also can be Ba 6ge 25the simple substance of compound and Cu and Ge.
S200: the reaction raw materials taken is put into crucible, and adds fusing assistant.
As preferably, crucible is the silica tube of plating carbon or does not plate the silica tube of carbon.
The temperature of fusion acting as reduction reaction raw materials of fusing assistant, promotes the carrying out of reaction.As preferably, the fusing point of the fusing assistant selected in the present invention is lower than the fusing point of the minimum component of fusing point in reaction raw materials.Preferably, the present invention selects heterogeneous fusing assistant Sn, and it at high temperature can not react with the reaction raw materials that takes in S100, and has relatively low fusing point, be beneficial in subsequent step with being separated of reaction product.
In addition, the present invention also can select In as fusing assistant, and the metal that other fusing points are lower also can be adopted as fusing assistant.
Preferably, the molar weight of fusing assistant is (1 ~ 8) with the ratio of the molar weight of Ba element in reaction raw materials: 1.
S300: the crucible sealed after being vacuumized of reaction raw materials and fusing assistant will be added with in S200.
The effect vacuumizing sealing prevents the air in reaction process from causing interference to fusing assistant, as reaction raw materials at high temperature can be oxidized by the oxygen in air, thus causes reacting and finally can not get required single crystal structure.
Preferably, the present invention adopts oxyhydrogen flame, oxy-acetylene flame, coal gas oxygen flame or argon plasma flame to seal quartz crucible.
S400: the crucible sealed in S300 is placed in High Temperature Furnaces Heating Apparatus, after being warming up to 900 DEG C ~ 1200 DEG C, insulation 12h ~ 72h, is then cooled to 250 DEG C ~ 700 DEG C, obtains the mixture of Runge-Kutta integration and fusing assistant.
Wherein, the Runge-Kutta integration obtained is single crystal structure, and chemical formula is Ba 8cu xge 46-x, x is mole coefficient, and 0.5≤x≤6.
It should be noted that, the High Temperature Furnaces Heating Apparatus in the present invention refers to the Reaktionsofen that can bear more than 1000 DEG C high temperature.
Preferably, the temperature rise rate in S400 and rate of temperature fall are respectively: be warming up to 900 DEG C ~ 1200 DEG C with the speed of 5 DEG C/min ~ 10 DEG C/min; 250 DEG C ~ 700 DEG C are cooled to the speed of 0.2 DEG C/h ~ 5 DEG C/h.
As another kind of embodiment, in S400, be warming up to 900 DEG C ~ 1200 DEG C with the speed of 5 DEG C/min ~ 10 DEG C/min, insulation 12h ~ 72h; Then two step coolings are divided:
Step 1. is cooled to 850 DEG C ~ 950 DEG C with the speed of 5 DEG C/h ~ 10 DEG C/h;
Step 2. is cooled to 250 DEG C ~ 700 DEG C with the speed of 0.2 DEG C/h ~ 5 DEG C/h.
It should be noted that, when the top temperature in temperature-rise period is 900 DEG C ~ 950 DEG C, be then cooled to the temperature value lower than the top temperature in temperature-rise period within the scope of 850 DEG C ~ 950 DEG C with the speed of 5 DEG C/h ~ 10 DEG C/h in the temperature-fall period of step 1.
S500: take out crucible at 250 DEG C ~ 700 DEG C, Runge-Kutta integration is separated with fusing assistant.
At 250 DEG C ~ 700 DEG C, fusing assistant is molten state, and Runge-Kutta integration is lenticular, thus, easier can realize being separated of fusing assistant and reaction product.As preferably, whizzer is utilized to be separated with fusing assistant by Runge-Kutta integration.
It should be noted that, separation herein refers to by centrifugal for fusing assistant on the inner side-wall of crucible, so with the crystal separation in crucible, in the process be separated with fusing assistant by Runge-Kutta integration, for preventing atmospheric oxidation, crucible is still in the state of sealing.
S600: the crucible after being separated fusing assistant is cooled to room temperature, takes out Runge-Kutta integration.
Aforesaid method is the growth directly will reaction raw materials being utilized to carry out monocrystalline, the preparation of Runge-Kutta integration monocrystalline can be completed without using polycrystalline presoma, save growth cost, the method preparation process is simple simultaneously, repetition rate is higher, the crystalline size obtained is also comparatively large, and crystal thermoelectricity capability ZT value can reach more than 0.6.
As another kind of embodiment, above-mentioned S200 also can replace in the following way:
S200 ＇: utilize the reaction raw materials taken in S100 to prepare polycrystalline presoma; Polycrystalline presoma is put into crucible, and adds fusing assistant.
Polycrystalline presoma is prepared by high temperature solid-state method: the reaction raw materials taken in S100 is put into crucible, by this crucible sealed after being vacuumized, then puts into High Temperature Furnaces Heating Apparatus sinter 4h ~ 8h at 950 DEG C ~ 1050 DEG C, obtain polycrystalline presoma.
Polycrystalline presoma is also prepared by the mode of melting: the reaction raw materials taken in S100 is put into crucible, this crucible is placed in induction furnace or electric arc furnace, pass into rare gas element or reducing gas, at 950 DEG C ~ 1050 DEG C, melting 4 ~ 8 hours, obtains polycrystalline presoma.Wherein, rare gas element can be argon gas, and reducing gas can be nitrogen hydrogen mixeding gas.
After preparing polycrystalline presoma by S200 ＇, then carry out according to the step of S300 ~ S600, finally obtain required monocrystalline Runge-Kutta integration.
It should be noted that, preparing the crucible that polycrystalline presoma adopts is not be same crucible with preparing the crucible that monocrystalline Runge-Kutta integration adopts.
In order to understand the present invention better, below by specific embodiment, Runge-Kutta integration of the present invention and preparation method thereof is further illustrated.
Embodiment 1
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:0.5:45.5, meanwhile, by granular fusing assistant Sn, according to being 1:1 with Ba simple substance mol ratio, ratio is weighed;
(2) the Ba simple substance taken, Cu simple substance, Ge simple substance and fusing assistant Sn are put into the silica tube not plating carbon;
(3) silica tube in step (2) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(4) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1200 DEG C of 5 DEG C/min, and is incubated 12h; Then 900 DEG C are cooled to the speed of 5 DEG C/h; Be cooled to 700 DEG C with the speed of 0.2 DEG C/h again, obtain Ba 8cu 0.5ge 45.5the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(5) at 700 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(6) silica tube is naturally cooled to room temperature, break silica tube into pieces, obtain the Ba being of a size of 20mm × 16mm × 14mm 8cu 0.5ge 45.5monocrystalline Runge-Kutta integration.
Embodiment 2
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:3:43, meanwhile, by granular fusing assistant Sn, according to being 3:1 with Ba simple substance mol ratio, ratio is weighed;
(2) the Ba simple substance taken, Cu simple substance, Ge simple substance and fusing assistant Sn are put into the silica tube not plating carbon;
(3) silica tube in step (2) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(4) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1100 DEG C of 5 DEG C/min, and is incubated 24h; Then 850 DEG C are cooled to the speed of 10 DEG C/h; 600 DEG C are cooled to again with the speed of 1 DEG C/h; Obtain Ba 8cu 3ge 43the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(5) at 600 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(6) silica tube is naturally cooled to room temperature, break silica tube into pieces, obtain the Ba being of a size of 19mm × 15mm × 12mm 8cu 3ge 43monocrystalline Runge-Kutta integration.
See Fig. 1, be the X-ray powder diffraction pattern of the Runge-Kutta integration that the present embodiment obtains, this collection of illustrative plates all has obvious diffraction peak in the peak position of 29 °, 30 ° and 31 ° degree, and illustrate that the material obtained belongs to isometric system, space group is
See Fig. 2 and Fig. 3, be respectively single crystal diffraction collection of illustrative plates and the laue photograph figure of the Runge-Kutta integration that the present embodiment obtains, can learn that this Runge-Kutta integration is single crystal structure by this two width figure.
The diffraction patterns of the Runge-Kutta integration obtained in other embodiments of the invention is all consistent with the present embodiment, illustrates that the material obtained is monocrystalline, and belongs to isometric system, and have space group.
Embodiment 3
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:6:40, meanwhile, by fusing assistant Sn, according to being 8:1 with Ba simple substance mol ratio, ratio is weighed;
(2) the Ba simple substance taken, Cu simple substance, Ge simple substance and fusing assistant Sn are put into the silica tube of plating carbon;
(3) silica tube in step (2) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(4) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 900 DEG C of 5 DEG C/min, and is incubated 72h; Then 250 DEG C are cooled to the speed of 2 DEG C/h; Obtain Ba 8cu 6ge 40the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(5) at 250 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(6) silica tube is naturally cooled to room temperature, break silica tube into pieces, take out crystal, obtain the Ba being of a size of 18mm × 14mm × 13mm 8cu 6ge 40monocrystalline Runge-Kutta integration.
Thermoelectric figure of merit (ZT) the variation with temperature figure of the Runge-Kutta integration that the black bars in Fig. 4 obtains for the present embodiment, as seen from the figure, Runge-Kutta integration ZT value when 773K reaches 0.65, has preferably thermoelectricity capability.
Embodiment 4
(1) by the Ba of bulk 6ge 25the ratio that compound, Cu simple substance and Ge simple substance are 8:12:64 according to mol ratio is weighed, and puts it in silica tube;
(2) by fusing assistant In, according to being 8:1 with Ba simple substance mol ratio, ratio is weighed; And added in the silica tube of step (1);
(3) silica tube in step (2) is vacuumized (vacuum tightness is 10 -3below torr), and utilize argon plasma flame to seal the silica tube exhausting vacuum;
(4) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1050 DEG C of 10 DEG C/min, and is incubated 72h; Then be cooled to 500 DEG C with the speed of 10 DEG C/h, obtain Ba 8cu 2ge 44the mixture of monocrystalline Runge-Kutta integration and fusing assistant In;
(5) at 500 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(6) silica tube is naturally cooled to room temperature, break silica tube into pieces, obtain the Ba being of a size of 18mm × 15mm × 12mm 8cu 2ge 44monocrystalline Runge-Kutta integration.
Embodiment 5
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:1:45, put it in open crucible;
(2) the open crucible in step (1) is placed in induction furnace, under argon gas atmosphere, at 950 DEG C of melting 4h, prepares Ba 8cuGe 45polycrystalline Runge-Kutta integration, and the Ba that will prepare 8cuGe 45polycrystalline Runge-Kutta integration puts into silica tube;
(3) ratio being 1:1 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cuGe 45in the silica tube of polycrystalline Runge-Kutta integration;
(4) silica tube in step (3) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(5) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1200 DEG C of 10 DEG C/min, and is incubated 12h; Then 850 DEG C are cooled to the speed of 8 DEG C/h; 700 DEG C are cooled to again with the speed of 3 DEG C/h; Obtain Ba 8cuGe 45the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(6) at 700 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(7) after isolation of crystalline and fusing assistant, silica tube is naturally cooled to room temperature, breaks silica tube into pieces, obtain the Ba being of a size of 16mm × 11mm × 11mm 8cuGe 45monocrystalline Runge-Kutta integration.
Embodiment 6
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:4:42, put it in open crucible;
(2) the open crucible in step (1) is placed in induction furnace, passes into argon gas, at 950 DEG C, melting 5h, prepares Ba 8cu 4ge 42polycrystalline Runge-Kutta integration, and the Ba that will prepare 8cu 4ge 42polycrystalline Runge-Kutta integration puts into silica tube;
(3) ratio being 1:3 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cu 4ge 42in the silica tube of polycrystalline Runge-Kutta integration;
(4) silica tube in step (3) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(5) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1100 DEG C of 8 DEG C/min, and is incubated 48h; Then 950 DEG C are cooled to the speed of 5 DEG C/h; Be cooled to 500 DEG C with the speed of 0.2 DEG C/h again, obtain Ba 8cu 4ge 42the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(6) at 500 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(7) after isolation of crystalline and fusing assistant, silica tube is naturally cooled to room temperature, breaks silica tube into pieces, obtain the Ba being of a size of 17mm × 12mm × 11mm 8cu 4ge 42monocrystalline Runge-Kutta integration.
Thermoelectric figure of merit (ZT) the variation with temperature curve of the Runge-Kutta integration that white circle obtains for the present embodiment in Fig. 4, as seen from the figure, Runge-Kutta integration ZT value when 773K, more than 0.63, has preferably thermoelectricity capability.
Embodiment 7
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:3:43, put it in open crucible;
(2) the open crucible in step (1) is placed in induction furnace, passes into argon gas, at 950 DEG C, melting 8h, prepares Ba 8cu 3ge 43polycrystalline Runge-Kutta integration, and the Ba that will prepare 8cu 3ge 43polycrystalline Runge-Kutta integration puts into silica tube;
(3) ratio being 1:4 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cu 3ge 43in the silica tube of polycrystalline Runge-Kutta integration;
(4) silica tube in step (3) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(5) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1200 DEG C of 10 DEG C/min, and is incubated 12h; Then 850 DEG C are cooled to the speed of 5 DEG C/h; Be cooled to 650 DEG C with the speed of 3 DEG C/h again, obtain Ba 8cu 3ge 43the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(6) at 650 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(7) after isolation of crystalline and fusing assistant, silica tube is naturally cooled to room temperature, breaks silica tube into pieces, obtain the Ba being of a size of 16mm × 11mm × 11mm 8cu 3ge 43caged monocrystalline.
Embodiment 8
(1) the Ba simple substance of bulk, Cu simple substance and Ge simple substance are weighed according to the ratio that mol ratio is 8:6:40, put it in open crucible;
(2) the open crucible in step (1) is placed in electric arc furnace, passes into argon gas, at 950 DEG C, melting 6h, prepares Ba 8cu 6ge 40polycrystalline Runge-Kutta integration, and the Ba that will prepare 8cu 6ge 40polycrystalline Runge-Kutta integration puts into silica tube;
(3) ratio being 1:8 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cu 6ge 40in the silica tube of polycrystalline Runge-Kutta integration;
(4) silica tube in step (3) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the silica tube exhausting vacuum;
(5) silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 900 DEG C of 10 DEG C/min, and is incubated 72h; Then be cooled to 250 DEG C with the speed of 0.2 DEG C/h, obtain Ba 8cu 6ge 40the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(6) at 250 DEG C, silica tube is taken out, and with whizzer, the crystal in silica tube is separated with fusing assistant.
(7) after isolation of crystalline and fusing assistant, silica tube is naturally cooled to room temperature, breaks silica tube into pieces, obtain the Ba being of a size of 16mm × 12mm × 10mm 8cu 6ge 40monocrystalline Runge-Kutta integration.
Embodiment 9
(1) by the Ba of bulk 6ge 25the ratio that compound, Cu simple substance and Ge simple substance are 8:24:52 according to mol ratio is weighed, and puts it in the first silica tube;
(2) the first silica tube in step (1) is vacuumized (vacuum tightness is 10 -3below torr), and utilize coal gas oxygen flame first silica tube to seal;
(3) the first silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, is heated to 950 DEG C, Temperature fall after insulation 12h, prepares Ba 8cu 4ge 42polycrystalline Runge-Kutta integration; Break the first silica tube into pieces and obtain Ba 8cu 4ge 42polycrystalline Runge-Kutta integration, and put it in the second silica tube;
(4) ratio being 1:6 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cu 4ge 42in second silica tube of polycrystalline Runge-Kutta integration;
(5) the second silica tube in step (4) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the second silica tube exhausting vacuum;
(6) the second silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 950 DEG C of 10 DEG C/min, and is incubated 48h; Then be cooled to 300 DEG C with the speed of 5 DEG C/h, obtain Ba 8cu 4ge 42the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(7) at 300 DEG C, the second silica tube is taken out, and with whizzer, the crystal in the second silica tube is separated with fusing assistant.
(8) after isolation of crystalline and fusing assistant, the second silica tube is naturally cooled to room temperature, breaks the second silica tube into pieces, obtain the Ba being of a size of 14mm × 13mm × 10mm 8cu 4ge 42monocrystalline Runge-Kutta integration.
Embodiment 10
(1) by the Ba of bulk 6ge 25the ratio that compound, Cu simple substance and Ge simple substance are 8:30:46 according to mol ratio is weighed, and puts it in the first silica tube;
(2) the first silica tube in step (1) is vacuumized (vacuum tightness is 10 -3below torr), and utilize coal gas oxygen flame first silica tube to seal;
(3) the first silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, is heated to 1050 DEG C, Temperature fall after insulation 12h, prepares Ba 8cu 5ge 41polycrystalline Runge-Kutta integration; And break the first silica tube into pieces and obtain Ba 8cu 5ge 41polycrystalline Runge-Kutta integration, and put it in the second silica tube;
(4) ratio being 1:4 according to Ba, Sn mol ratio takes fusing assistant Sn; The fusing assistant Sn taken is joined Ba is housed 8cu 5ge 41the second silica tube in;
(5) the second silica tube in step (4) is vacuumized (vacuum tightness is 10 -3below torr), and utilize oxy-acetylene flame to seal the second silica tube exhausting vacuum;
(6) the second silica tube of sealing is placed in High Temperature Furnaces Heating Apparatus, with the ramp to 1100 DEG C of 10 DEG C/min, and is incubated 54h; Then be cooled to 300 DEG C with the speed of 3 DEG C/h, obtain Ba 8cu 5ge 41the mixture of monocrystalline Runge-Kutta integration and fusing assistant Sn;
(7) at 300 DEG C, the second silica tube is taken out, and with whizzer, the crystal in the second silica tube is separated with fusing assistant.
(8) after isolation of crystalline and fusing assistant, the second silica tube is naturally cooled to room temperature, breaks the second silica tube into pieces, obtain the Ba being of a size of 12mm × 11mm × 10mm 8cu 5ge 41monocrystalline Runge-Kutta integration.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a Runge-Kutta integration, is characterized in that, the chemical formula of described Runge-Kutta integration is Ba 8cu xge 46-x, wherein, x is mole coefficient, and 0.5≤x≤6; And described Runge-Kutta integration is monocrystalline.
2. Runge-Kutta integration according to claim 1, is characterized in that, described Runge-Kutta integration belongs to isometric system, and space group is
3. a preparation method for the Runge-Kutta integration described in claim 1 or 2, is characterized in that, comprises the following steps:
S100: take the reaction raw materials containing Ba element, Cu element and Ge element according to the stoichiometric ratio of component each in described Runge-Kutta integration;
S200: the described reaction raw materials taken is put into crucible, and adds fusing assistant; Or the reaction raw materials taken described in first utilizing prepares polycrystalline presoma, more described polycrystalline presoma is put into crucible, and add fusing assistant;
S300: by the described crucible sealed after being vacuumized being added with fusing assistant;
S400: the crucible of described sealing is placed in High Temperature Furnaces Heating Apparatus, after being warming up to 900 DEG C ~ 1200 DEG C, insulation 12h ~ 72h, is then cooled to 250 DEG C ~ 700 DEG C, obtains the mixture of Runge-Kutta integration and fusing assistant;
S500: take out described crucible at 250 DEG C ~ 700 DEG C, described Runge-Kutta integration is separated with described fusing assistant;
S600: described crucible is cooled to room temperature, takes out described Runge-Kutta integration.
4. preparation method according to claim 3, is characterized in that, in S200, the reaction raw materials taken described in utilization is prepared polycrystalline presoma and comprised the following steps:
The described reaction raw materials taken is put into crucible, by described crucible sealed after being vacuumized, then puts into High Temperature Furnaces Heating Apparatus sinter 4h ~ 8h at 950 DEG C ~ 1050 DEG C, obtain polycrystalline presoma;
Or the described reaction raw materials taken is put into crucible, be placed in induction furnace or electric arc furnace, pass into rare gas element or reducing gas, at 950 DEG C ~ 1050 DEG C, melting 4 ~ 8 hours, obtains polycrystalline presoma.
5. preparation method according to claim 3, is characterized in that, described reaction raw materials is the simple substance of Ba, Cu, Ge, or Ba 6ge 25the simple substance of compound and Cu and Ge.
6. preparation method according to claim 3, is characterized in that, in S400, is warming up to 900 DEG C ~ 1200 DEG C with the speed of 5 DEG C/min ~ 10 DEG C/min;
250 DEG C ~ 700 DEG C are cooled to the speed of 0.2 DEG C/h ~ 5 DEG C/h; Or after being first cooled to 850 DEG C ~ 950 DEG C with the speed of 5 DEG C/h ~ 10 DEG C/h, then be cooled to 250 DEG C ~ 700 DEG C with the speed of 0.2 DEG C/h ~ 5 DEG C/h.
7. preparation method according to claim 3, is characterized in that, described fusing assistant is Sn or In.
8. preparation method according to claim 3, is characterized in that, in S200, the molar weight of the fusing assistant of described interpolation is (1 ~ 8) with the ratio of the molar weight of Ba element in the described reaction raw materials taken: 1.
9. preparation method according to claim 3, is characterized in that, in S300, adopts oxyhydrogen flame, oxy-acetylene flame, coal gas oxygen flame or argon plasma flame to seal described crucible.
10. the application of Runge-Kutta integration in Thermoelectric Generator or thermoelectric cooling device described in a claim 1 or 2.
CN201410424124.2A 2014-08-26 2014-08-26 Runge-Kutta integration and its preparation method and application Active CN104328500B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410424124.2A CN104328500B (en) 2014-08-26 2014-08-26 Runge-Kutta integration and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410424124.2A CN104328500B (en) 2014-08-26 2014-08-26 Runge-Kutta integration and its preparation method and application

Publications (2)

Publication Number Publication Date
CN104328500A true CN104328500A (en) 2015-02-04
CN104328500B CN104328500B (en) 2017-06-09

Family

ID=52403304

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410424124.2A Active CN104328500B (en) 2014-08-26 2014-08-26 Runge-Kutta integration and its preparation method and application

Country Status (1)

Country Link
CN (1) CN104328500B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113443632A (en) * 2020-03-24 2021-09-28 丰田自动车株式会社 Method for producing Si-based active material
CN115573027A (en) * 2021-06-21 2023-01-06 南京理工大学 Preparation of Cr 7 Se 8 Method for single crystal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101393959A (en) * 2008-11-07 2009-03-25 中国科学院上海硅酸盐研究所 Cage type compound
CN101979688A (en) * 2010-08-26 2011-02-23 中国科学院宁波材料技术与工程研究所 SiO2 nanoparticle composite cage compound thermoelectric material and preparation method thereof
CN102031415A (en) * 2009-09-28 2011-04-27 中国科学院福建物质结构研究所 Type I stibium-based clathrate materials and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101393959A (en) * 2008-11-07 2009-03-25 中国科学院上海硅酸盐研究所 Cage type compound
CN102031415A (en) * 2009-09-28 2011-04-27 中国科学院福建物质结构研究所 Type I stibium-based clathrate materials and preparation method thereof
CN101979688A (en) * 2010-08-26 2011-02-23 中国科学院宁波材料技术与工程研究所 SiO2 nanoparticle composite cage compound thermoelectric material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HUI ZHANG,ET AL.: "Structure and low temperature physical properties of Ba8Cu6Ge40", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
JING-HAN CHEN，ET AL.: "NMR and computational study of Ba8CuxGe46-x clathrate semiconductors", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
SIMON JOHNSEN,ET AL.: "Crystal Structure, Band Structure, and Physical Properties of Ba8Cu6-xGe40+x (0 ≤x≤0.7)", 《CHEM. MATER.》 *
YANG LI, ET AL.: "Structure and stability of Ba–Cu–Ge type-I clathrates", 《J. PHYS.: CONDENS. MATTER》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113443632A (en) * 2020-03-24 2021-09-28 丰田自动车株式会社 Method for producing Si-based active material
CN113443632B (en) * 2020-03-24 2023-11-07 丰田自动车株式会社 Method for producing Si-based active material
CN115573027A (en) * 2021-06-21 2023-01-06 南京理工大学 Preparation of Cr 7 Se 8 Method for single crystal
CN115573027B (en) * 2021-06-21 2024-03-19 南京理工大学 Cr preparation 7 Se 8 Method for producing single crystals

Also Published As

Publication number Publication date
CN104328500B (en) 2017-06-09

Similar Documents

Publication Publication Date Title
CN108238796B (en) Copper seleno solid solution thermoelectric material and preparation method thereof
CN107799646B (en) Alloy thermoelectric semiconductor material and preparation method thereof
CN102786089B (en) Production method of zinc arsenide
CN110184654A (en) A kind of Bi2O2Se crystal and preparation method thereof
CN107235477A (en) A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof
CN107845724A (en) A kind of low cost environment friendly SnS base thermoelectricity materials and preparation method thereof
CN108447972A (en) A kind of SnTe base high-performances thermoelectric material and preparation method thereof
CN109851360B (en) P-type bismuth telluride-based bulk thermoelectric material (Bi)1-xSbx）2Te3Preparation method of (1)
CN104498751A (en) Preparation method of thermoelectric material of skutterudite
CN104004935B (en) A kind of method of supper-fast preparation high-performance high manganese-silicon thermoelectric material
CN110408989B (en) Oxide thermoelectric material BiCuSeO monocrystal and preparation method thereof
CN104328500A (en) Clathrate, preparation method and applications thereof
CN111200055A (en) High-performance PbTe-based N-type thermoelectric material and preparation method thereof
CN108735887B (en) Antimony-doped high-performance GeTe-PbTe solid solution thermoelectric material and preparation method thereof
CN101217178A (en) A preparation method for antimonide molybdenum base thermoelectric material
CN108417704A (en) A kind of high-performance mixes europium PbTe base thermoelectricity materials and preparation method thereof
CN107359231B (en) Low-heat-conduction Geranite thermoelectric material and preparation method thereof
CN103290249B (en) Produce the method for the method of thermo-electric converting material, device and production sputtering target material
CN101857929A (en) Zinc antimony based porous p-type thermoelectric material and preparation method thereof
CN109022863B (en) Ga-filled skutterudite thermoelectric material and preparation method thereof
CN109904304A (en) A kind of perovskite structure thermoelectric material CsMX3Preparation method
CN111048658A (en) SnI2Doped CsGeI3Perovskite thermoelectric material and preparation method thereof
CN109103323A (en) A method of Sb is replaced by filling Ga, Te and improves based square cobalt mineral conducting material thermoelectricity performance
CN108511588A (en) A kind of MnTe2Base novel thermoelectric material and preparation method thereof
CN111653662B (en) GeTe-based thermoelectric material with pseudo-cubic phase structure and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant