CN108063179A - A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof - Google Patents
A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN108063179A CN108063179A CN201711381581.8A CN201711381581A CN108063179A CN 108063179 A CN108063179 A CN 108063179A CN 201711381581 A CN201711381581 A CN 201711381581A CN 108063179 A CN108063179 A CN 108063179A
- Authority
- CN
- China
- Prior art keywords
- minutes
- powder
- silicon
- thermoelectric material
- nanocrystalline
- 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
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
Abstract
The present invention relates to a kind of nanocrystalline porous buik silicon block thermoelectric materials and preparation method thereof, belong to field of thermoelectric material technique.The material structure formula is BxSi or SbxSi (0.01≤x≤0.3), grain size range are 5~200nm, and pore diameter range is 10~100nm.Preparation method of the present invention is using diatomite as raw material, sodium chloride is grain refiner, magnesium is reducing agent, after 650 DEG C of reduction, is washed by washing, dilute hydrochloric acid, hydrofluoric acid wash, porous silicon manocrystalline powders are obtained after rotary evaporation vacuum drying, it is polished by adding boron and antimony, obtain mixing thermoelectricity powder, again by 40MPa, nanocrystalline porous silicon bulk thermoelectric material is obtained after 1000 DEG C of discharge plasma sinterings.Silicon thermoelectric material prepared by this method is provided simultaneously with nanocrystalline structure and porous structure, has the thermal conductivity of two orders of magnitude lower than monocrystalline silicon.
Description
Technical field
The invention belongs to thermoelectric energy transition material technical fields, and in particular to a kind of nanocrystalline porous buik silicon thermoelectricity material
Material and preparation method thereof,.
Background technology
Thermoelectric material be exactly using the temperature difference drive carrier move from temperature end to low temperature the electrical potential difference of aggregation formation come
It generates electricity or moves to carry out the material of neither endothermic nor exothermic between the material of different energy levels using electrical potential difference driving carrier
Material.The material has many advantages, such as pollution-free, noiseless during movement-less part, use, mainly applied to various electronics devices
Isotope thermo-electric generation etc. in the refrigeration of part, the exhaust heat recovery power generation of gas engine, the manned astro-engineering.At present, it is common
Room temperature thermoelectric material is bismuth telluride, and middle warm area is antimony cobalt, lead telluride and the SiGe of high-temperature region.They usually have higher
The features such as electrical conductivity and Seebeck coefficient, relatively low thermal conductivity.Above-mentioned widely used thermoelectric material usually by rare, expensive or
The toxic heavy element such as compositions such as bismuth, lead, tellurium, cobalt, antimony, and really industrialize a large amount of low costs of needs, environmental protection, nontoxic heat
Electric material.Silicon is most widely used semiconductor, resourceful and nontoxic, and with for inexpensive high yield production
Large scale industry infrastructure.It is very tempting that silicon is made, which to become a kind of thermoelectric material, but the thermal conductivity of silicon is too high, it is difficult to generate foot
The big temperature difference is reached to form significant electrical potential difference.It is almost complete as the covalent bonding semiconductor crystallized in diamond lattic structure
The heat in silicon is transferred full by lattice vibration, electron conducting part is minimized.The nanosizing and porous of silicon have been demonstrated
It is to enhance the effective ways that phon scattering inhibits lattice thermal conductivity.For nanosizing, thermoelectricity nanocrystal is with nanometer at present
Powder starts as raw material, is prepared by bottom-to-top method.In general, raw material powder is by ball milling metallicity silica flour
End manufacture, of high cost, high energy consumption.For porous, etching anode is the common technology of silicon pore-creating at present.Porous can be with
By the way that anodic oxidation semiconductor obtains under suitable conditions in suitable electrolyte.It is added based on metallicity silicon
Work, it is of high cost, and etching anode is simply possible to use in production porous silicon film, can not prepare porous silicon bulk.Therefore there is an urgent need to seek
A kind of environmentally friendly and energy saving method is asked to carry out silicon nanosizing and pore-creating, prepares nanocrystalline porous silicon materials.
The content of the invention
The purpose of the present invention is to propose to a kind of using diatomite as the nanocrystalline porous block silicon thermoelectric material and its system of raw material
Preparation Method with the thermal conductivity for reducing production cost, reducing silicon, obtains certain thermoelectricity output performance.
Nanocrystalline porous block silicon thermoelectric material proposed by the present invention, chemical structural formula BxSi or SbxSi, wherein
0.01≤x≤0.3, grain size range are 5~200nm, and pore diameter range is 10~100nm.
The preparation method of above-mentioned nanocrystalline porous block silicon thermoelectric material comprises the following steps：
(1) according to 10:1 weight ratio, weighs sodium chloride and diatomite powder respectively；The sodium chloride is configured to
The diatomite is added in sodium-chloride water solution, and stirred 10-30 minutes by the sodium-chloride water solution of 1mol/L, is mixed
Liquid；Above-mentioned mixed liquor is carried out at 120 DEG C rotary evaporation in vacuo 12-24 it is small when, obtain mixed-powder；
(2) above-mentioned dry mixed powder is ground 10-30 minutes in mortar, by dry mixed powder：Magnesium powder=11：
0.9 weight ratio weighs and adds the magnesium powder of such weight, obtained mixed-powder is further ground 10-30 minutes, is obtained
To mixture；
(3) mixture is transferred in graphite crucible, mixture is transferred in atmosphere furnace, logical high-purity argon protection gas, 5 points
Clock is warming up to 650 DEG C, when heat preservation 2-5 is small, mixture after being reduced；
(4) batch mixing after above-mentioned reduction is added in centrifuge tube, deionized water is added in, with 2000 rpms of centrifuge washings
10 minutes, supernatant liquor is removed, repeats washing 2 times；Then the dilute hydrochloric acid of 1mol/L is added in, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times；5vol% hydrofluoric acid is eventually adding, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times, obtain mixing wet feed；
(5) by above-mentioned mixing wet feed, when 60 DEG C of vacuum drying 12 are small after, according to stoichiometric ratio BxSi or SbxSi
(0.01≤x≤0.3) weighs and adds in the boron or antimony of such weight, mixed-powder is transferred in agate mortar and grinds 10-30
Minute, 550 DEG C are then heated within 5 minutes by discharge plasma sintering, 550 DEG C are kept for 20 minutes, are then heated within 5 minutes
It 1000 DEG C, is kept for 5 minutes under pressure 40MPa, obtains nanocrystalline porous block silicon thermoelectric material.
Nanocrystalline porous block silicon thermoelectric material proposed by the present invention and preparation method thereof, advantage is：Made with diatomite
For raw material, diatomite is cheap, natural abundant, non-toxic, and cost, while useful environment can be greatly reduced；Using magnesium also
Former diatomite only requires heat to 650 DEG C and can obtain porous silicon, and 2000 DEG C of profits are heated in electric arc furnaces compared to conventional
The silicon technology of preparing of silica is reduced with charcoal and coke, substantial amounts of electric power energy can be saved.Utilize the method for the present invention
The silicon thermoelectric material of preparation is provided simultaneously with nanocrystalline structure and porous structure, has the thermal conductivity of two orders of magnitude lower than monocrystalline silicon
Rate.Therefore, nanocrystalline porous block silicon thermoelectric material of the invention is a kind of thermoelectric material with applications well prospect.
Description of the drawings
Fig. 1 is the porous silicon bulk X-ray diffractogram of the various heterogeneities prepared using the method for the present invention.
Fig. 2 is the B prepared using the method for the present invention0.1The profile scanning electron microscope of the nanocrystalline porous silicon bulks of Si.
Fig. 3 is the B prepared using the method for the present invention0.1The section transmission electron microscope picture of the nanocrystalline porous silicon bulks of Si.
Fig. 4 is the electrical conductivity variation with temperature of the porous silicon bulk of the various heterogeneities prepared using the method for the present invention
Relational graph.
Fig. 5 be using the method for the present invention prepare various heterogeneities porous silicon bulk Seebeck coefficient absolute value with
The variation relation figure of temperature.
Fig. 6 is the lattice thermal conductivity of the porous silicon bulk of the various heterogeneities prepared using the method for the present invention with temperature
Variation relation figure.
Fig. 7 is the thermoelectric figure of merit of the porous silicon bulk of the various heterogeneities prepared using the method for the present invention with the change of temperature
Change relational graph.
Specific embodiment
Nanocrystalline porous block silicon thermoelectric material proposed by the present invention, chemical structural formula BxSi or SbxSi, wherein
0.01≤x≤0.3, grain size range are 5~200nm, and pore diameter range is 10~100nm.
The preparation method of above-mentioned nanocrystalline porous block silicon thermoelectric material comprises the following steps：
(1) according to 10:1 weight ratio, weighs sodium chloride and diatomite powder respectively；The sodium chloride of above-mentioned weight is configured
For the sodium-chloride water solution of 1mol/L, the diatomite of above-mentioned weight is added in sodium-chloride water solution, and is stirred 10-30 minutes,
Obtain mixed liquor；Above-mentioned mixed liquor is carried out at 120 DEG C rotary evaporation in vacuo 12-24 it is small when, obtain mixed-powder；
(2) above-mentioned dry mixed powder is ground 10-30 minutes in mortar, by dry mixed powder：Magnesium powder=11：
0.9 weight ratio weighs and adds the magnesium powder of such weight, obtained mixed-powder is further ground 10-30 minutes, is obtained
To mixture；
(3) mixture is transferred in graphite crucible, mixture is transferred in atmosphere furnace, logical high-purity argon protection gas, 5 points
Clock is warming up to 650 DEG C, when heat preservation 2-5 is small, mixture after being reduced；
(4) batch mixing after above-mentioned reduction is added in centrifuge tube, deionized water is added in, with 2000 rpms of centrifuge washings
10 minutes, supernatant liquor is removed, repeats washing 2 times；Then the dilute hydrochloric acid of 1mol/L is added in, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times；5vol% hydrofluoric acid is eventually adding, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times, obtain mixing wet feed；
(5) by above-mentioned mixing wet feed, when 60 DEG C of vacuum drying 12 are small after, according to stoichiometric ratio BxSi or SbxSi
(0.01≤x≤0.2) weighs and adds in the boron and antimony of such weight, mixed-powder is transferred in agate mortar and grinds 10-30
Minute, then by being heated within 5 minutes 550 DEG C by discharge plasma sintering, 550 DEG C are kept for 20 minutes, are then heated within 5 minutes
To 1000 DEG C, kept for 5 minutes under pressure 40MPa, obtain nanocrystalline porous block silicon thermoelectric material.
The lattice thermal conductivity of the nanocrystalline porous silicon thermoelectric material prepared using the present invention is in 14W/mK~7W/mK
(room temperature~727 DEG C), thermoelectric figure of merit are 0.001~0.09 (room temperature~727 DEG C).For example, Fig. 1 is B0.2Si and Sb0.2Si blocks
The X-ray diffractogram of material is treated as be divided into B as seen from Figure 10.2During Si, for the pure phase of Si, ingredient Sb0.1During Si, there is one
Fixed Sb is precipitated；B0.2The interface scanning Electronic Speculum of Si blocks is as shown in Fig. 2, as shown in Figure 2, sintered block exists a large amount of
Nano-pore, size range 10-100nm.Fig. 3 is B0.2The interface transmission electron microscope picture of Si blocks, it can be seen that in material
Si crystal grain be nano-scale, size range 5-200nm.As embodiment, Fig. 4 is the B of synthesis0.1Si and Sb0.2Si materials
Electrical conductivity, it can be seen that ingredient B0.2The nanocrystalline porous silicon thermoelectric material electrical conductivity of Si is relatively high.Fig. 5 be synthesis into
B0.2Si and Sb0.2The Seebeck coefficient absolute value of Si materials, it can be seen that Sb0.2The nanocrystalline porous silicon thermoelectric material match of Si
Seebeck coefficient absolute value is relatively high.Fig. 6 is the B of synthesis0.2Si and Sb0.2The lattice thermal conductivity of Si materials, it can be seen that ingredient
For B0.2The lattice thermal conductivity of Si is relatively low, two orders of magnitude lower than the thermal conductivity of monocrystalline silicon, and lower thermal conductivity is conducive to improve the heat of material
The electric figure of merit.Fig. 7 is the B of synthesis0.2Si and Sb0.2The thermoelectric figure of merit of Si materials, it can be seen that B0.1The thermoelectric figure of merit of Si materials is opposite
It is higher, reach 0.08 at 727 DEG C.
The present invention is described in more detail with reference to the accompanying drawings and examples.
Embodiment 1
Preparation chemical composition is B0.1The nanocrystalline porous silicon thermoelectric material of Si：
A. according to 10:1 weight ratio, weighs sodium chloride and diatomite powder respectively；The sodium chloride of above-mentioned weight is configured
For the sodium-chloride water solution of 1mol/L, the diatomite of above-mentioned weight is added in sodium-chloride water solution, and is stirred 10-30 minutes,
Obtain mixed liquor；Above-mentioned mixed liquor is carried out at 120 DEG C rotary evaporation in vacuo 12-24 it is small when, obtain mixed-powder；
B. above-mentioned dry mixed powder is ground 10-30 minutes in mortar, by dry mixed powder：Magnesium powder=11：0.9
Weight ratio, weigh and add the magnesium powder of above-mentioned weight, obtained mixed-powder is further ground 10-30 minutes, is obtained
Mixture；
C. mixture is transferred in graphite crucible, mixture is transferred in atmosphere furnace, logical high-purity argon protection gas, 5 points
Clock is warming up to 650 DEG C, when heat preservation 2-5 is small, mixture after being reduced；
D. batch mixing after above-mentioned reduction is added in centrifuge tube, deionized water is added in, with 2000 rpms of centrifuge washings
10 minutes, supernatant liquor is removed, repeats washing 2 times；Then the dilute hydrochloric acid of 1mol/L is added in, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times；5vol% hydrofluoric acid is eventually adding, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times, obtain mixing wet feed；
E. by above-mentioned mixing wet feed, when 60 DEG C of vacuum drying 12 are small after, according to stoichiometric ratio B0.1Si is weighed and added
Enter the boron of such weight, mixed-powder is transferred in agate mortar and is ground 10-30 minutes, then passes through discharge plasma sintering
550 DEG C are heated within 5 minutes, 550 DEG C are kept for 20 minutes, are then heated to 1000 DEG C within 5 minutes, and 5 points are kept under pressure 40MPa
Clock obtains nanocrystalline porous block silicon thermoelectric material.
Embodiment 2
Preparation chemical composition is Sb0.1The nanocrystalline porous silicon thermoelectric material of Si：
A. according to 10:1 weight ratio, weighs sodium chloride and diatomite powder respectively；The sodium chloride of above-mentioned weight is configured
For the sodium-chloride water solution of 1mol/L, the diatomite of above-mentioned weight is added in sodium-chloride water solution, and is stirred 10-30 minutes,
Obtain mixed liquor；Above-mentioned mixed liquor is carried out at 120 DEG C rotary evaporation in vacuo 12-24 it is small when, obtain mixed-powder；
B. above-mentioned dry mixed powder is ground 10-30 minutes in mortar, by dry mixed powder：Magnesium powder=11：0.9
Weight ratio, weigh and add the magnesium powder of above-mentioned weight, obtained mixed-powder is further ground 10-30 minutes, is obtained
Mixture；
C. mixture is transferred in graphite crucible, mixture is transferred in atmosphere furnace, logical high-purity argon protection gas, 5 points
Clock is warming up to 650 DEG C, when heat preservation 2-5 is small, mixture after being reduced；
D. batch mixing after above-mentioned reduction is added in centrifuge tube, deionized water is added in, with 2000 rpms of centrifuge washings
10 minutes, supernatant liquor is removed, repeats washing 2 times；Then the dilute hydrochloric acid of 1mol/L is added in, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times；5vol% hydrofluoric acid is eventually adding, is washed with 2000 rpms of centrifugations
It washs 10 minutes, removes supernatant liquor, repeat washing 2 times, obtain mixing wet feed；
By above-mentioned mixing wet feed, when 60 DEG C of vacuum drying 12 are small after, according to stoichiometric ratio Sb0.1Si is weighed and added in
Mixed-powder is transferred in agate mortar and grinds 10-30 minutes, then passes through discharge plasma sintering 5 by the antimony of such weight
Minute is heated to 550 DEG C, and 550 DEG C are kept for 20 minutes, are then heated to 1000 DEG C within 5 minutes, are kept for 5 minutes under pressure 40MPa,
Obtain nanocrystalline porous block silicon thermoelectric material.
Technical scheme is described in detail in above-described embodiment.It is apparent that the present invention is not limited it is retouched
The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint
What is equal with the present invention or similar variation belongs to the scope of protection of the invention.
Claims (10)
1. a kind of nanocrystalline porous block silicon thermoelectric material, which is characterized in that the chemical structural formula of the thermoelectric material is BxSi or
SbxSi, wherein 0.01≤x≤0.3, grain size range is 5~200nm, and pore diameter range is 10~100nm.
2. the preparation method of nanocrystalline porous block silicon thermoelectric material described in claim 1, which is characterized in that including following step
Suddenly：
A. sodium chloride and diatomite powder are weighed；Sodium-chloride water solution is configured, the diatomite is added in sodium-chloride water solution
Stirring, obtains mixed liquor；Gained mixed liquor is subjected to rotary evaporation in vacuo, obtains mixed-powder；
B. mixed-powder is pressed after above-mentioned mixed-powder is ground：Magnesium powder=11：0.9 weight ratio weighs mixing further grinding,
Obtain mixture；
C. above-mentioned mixture is poured into graphite crucible to be put into atmosphere furnace, leads to argon gas, be warming up to 650 DEG C, when heat preservation 2-5 is small, obtain
Mixture after to reduction；
D. mixture after above-mentioned reduction is put into centrifuge tube, adds deionized water, centrifuge washing removes clear liquid, then adds in dilute salt
Acid, centrifuge washing remove clear liquid, are eventually adding hydrofluoric acid, and centrifuge washing removes clear liquid, obtain mixing wet feed；
E. by above-mentioned mixing wet feed, after vacuum drying, according to stoichiometric ratio BxSi or SbxSi (0.01≤x≤0.2) is added in should
Etc. weight boron or antimony, mixed-powder is ground, then by discharge plasma sintering, obtains nanocrystalline porous buik silicon thermoelectricity
Material.
3. method according to claim 2, which is characterized in that the weight ratio of sodium chloride and diatomite powder described in step a
For 10:1, the concentration of the sodium-chloride water solution is 1mol/L, and the time of the stirring is 10-30 minutes.
4. method according to claim 2, which is characterized in that milling time described in step b is 10-30 minutes.
5. method according to claim 2, which is characterized in that it heats up described in step c and completes in 5 minutes,.
6. method according to claim 2, which is characterized in that the rotating speed of centrifuge washing described in step d is 2000 revs/min
Clock, time are 10 minutes.
7. method according to claim 2, which is characterized in that the concentration of dilute hydrochloric acid described in step d be 1mol/L, the hydrogen
The concentration of fluoric acid is 5vol%.
8. method according to claim 2, which is characterized in that vacuum drying condition is 60 DEG C described in step e, and 12 is small
When.
9. method according to claim 2, which is characterized in that the condition of discharge plasma sintering described in step e is 5 minutes
550 DEG C are heated to, is kept for 20 minutes, is then heated within 5 minutes 1000 DEG C, is kept for 5 minutes.
10. method according to claim 9, which is characterized in that kept described in step e be within 5 minutes under the conditions of 40MPa into
Row.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711381581.8A CN108063179B (en) | 2017-12-20 | 2017-12-20 | A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711381581.8A CN108063179B (en) | 2017-12-20 | 2017-12-20 | A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108063179A true CN108063179A (en) | 2018-05-22 |
| CN108063179B CN108063179B (en) | 2019-05-31 |
Family
ID=62139374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711381581.8A Active CN108063179B (en) | 2017-12-20 | 2017-12-20 | A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108063179B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828809A (en) * | 2019-11-20 | 2020-02-21 | 厦门大学 | Silicon-carbon composite material in form of bubble coral and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2305728C3 (en) * | 1972-04-27 | 1978-09-14 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Screen-printable, glass-containing mass suitable for the production of electrical switching devices, in particular thermistor elements, which can be burned in in air |
| CN102603348A (en) * | 2012-03-14 | 2012-07-25 | 刘相红 | Nano-pore heat-insulation material and manufacturing method thereof |
| CN103649011A (en) * | 2011-05-03 | 2014-03-19 | 英诺瓦莱特公司 | Ceramic boron-containing doping paste and methods therefor |
-
2017
- 2017-12-20 CN CN201711381581.8A patent/CN108063179B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2305728C3 (en) * | 1972-04-27 | 1978-09-14 | E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) | Screen-printable, glass-containing mass suitable for the production of electrical switching devices, in particular thermistor elements, which can be burned in in air |
| CN103649011A (en) * | 2011-05-03 | 2014-03-19 | 英诺瓦莱特公司 | Ceramic boron-containing doping paste and methods therefor |
| CN102603348A (en) * | 2012-03-14 | 2012-07-25 | 刘相红 | Nano-pore heat-insulation material and manufacturing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828809A (en) * | 2019-11-20 | 2020-02-21 | 厦门大学 | Silicon-carbon composite material in form of bubble coral and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108063179B (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101656292B (en) | Preparation method for bismuth-tellurium nano-porous thermoelectric material | |
| CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
| CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
| KR20110052225A (en) | Nanocomposite thermoelectric material, and thermoelectric device and thermoelectric module comprising same | |
| CN108231991A (en) | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat | |
| CN102031416B (en) | Composite material of skutterudite filling substrate and preparation method thereof | |
| CN101435029A (en) | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material | |
| CN107400917A (en) | A kind of SnSe2Crystalline compounds and its preparation method and application | |
| CN107123729B (en) | A kind of nanometer silicon carbide/P-type silicon germanium alloy base thermoelectrical composite material and preparation method thereof | |
| CN102280570A (en) | Trace Cu-doped Bi2S3-based thermoelectric material | |
| CN110078476A (en) | A kind of Al doping BiCuSeO base thermoelectricity material and preparation method thereof | |
| CN106145062B (en) | A kind of quick method for preparing antimony telluride thermoelectric material | |
| CN100560487C (en) | A kind of method of low-temperature preparation of cubic silicon carbide nano wire | |
| CN108063179B (en) | A kind of nanocrystalline porous block silicon thermoelectric material and preparation method thereof | |
| CN106033790B (en) | A kind of Cu2-xSe/ graphene composite materials and preparation method thereof | |
| CN106159076B (en) | A kind of Cu2-xThe preparation method of Se/ graphene composite materials | |
| CN106098922B (en) | A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials | |
| CN108807654A (en) | High-performance and low-cost MnGeTe2Base thermoelectricity material and its preparation | |
| CN104047059B (en) | Prepare the Cu of thermoelectric material3sbSe4nanocrystal and synthetic method thereof | |
| CN104103750B (en) | Preparation method of magnesium-silicon based silicon nanowire composite thermoelectric material | |
| CN106283173A (en) | A kind of method reducing Tellurobismuthite. polycrystalline lattice thermal conductivity | |
| CN110218888A (en) | A kind of novel Zintl phase thermoelectric material and preparation method thereof | |
| CN105932148B (en) | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials | |
| CN104946918A (en) | New method for quickly preparing AgInSe2 based thermoelectric material | |
| CN108172680B (en) | Cubic phase Ca2Ge thermoelectric material and preparation method thereof |
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 |