CN101157139A - A preparation method of Ag complex Ca*Co**O** base oxide pyroelectric material - Google Patents
A preparation method of Ag complex Ca*Co**O** base oxide pyroelectric material Download PDFInfo
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- CN101157139A CN101157139A CNA2007101446429A CN200710144642A CN101157139A CN 101157139 A CN101157139 A CN 101157139A CN A2007101446429 A CNA2007101446429 A CN A2007101446429A CN 200710144642 A CN200710144642 A CN 200710144642A CN 101157139 A CN101157139 A CN 101157139A
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Abstract
The invention discloses a preparation method of Ag compound Ca9 Co12O28-based oxide thermoelectric material, and relates to the preparation method of Ag compound Ca-Co-O-based oxide thermoelectric material. The invention resolves the problems that the distribution of Ag phases in an Ag compound Ca-Co-O-based oxide is uneven and the Ag phases are easy to be reunited, the sizes of Ag phase particles are large, thereby leading that current carrier transporting loop is formed between Ca-Co-O-based oxide crystal grains, and leading Seebeck coefficient of the Ag compound Ca-Co-O-based oxide to be reduced evidently. The preparation methods comprises that firstly, soluble Ca<2 +> salt and soluble Co<2 +>salt are dissolved in distilled water; secondly, citric acid is added; thirdly, silver nitrate is added; fourthly, organic monomers and network agent are added; fifthly, initiating agent is added; sixthly, the microwave dry is performed; seventhly, calcination is operated; eighthly, the spark plasma sintering is performed, and then the Ag compound Ca9Co12O28-based oxide thermoelectric material is obtained. The distribution of Ag phases in Ag compound Ca9Co12O28is even, the size of the Ag phase particles is smaller than 500 nm, and the current carrier transporting loop is not formed. The Seebeck coefficient of the Ag compound Ca9Co12O28-based oxide thermoelectric material improves 2.7 percent to 7.1 percent than that of the Ca9Co12O28, the electrical conductivity improves 21.1 percent to 42.1 percent, and the power factor improves 27.8 percent to 63.0 percent.
Description
Technical field
The present invention relates to the preparation method of a kind of Ag complex Ca-Co-O base oxide pyroelectric material.
Background technology
Along with becoming increasingly conspicuous of energy and environment problem, this thermoelectric transformation technology of waste-heat power generation receives increasing concern as applied widely with the new energy technology that meets environment protection requirement, and is significant for developing a circular economy, building a conservation-minded society.The Ca-Co-O base oxide is the elevated temperature heat electric material that is widely used at industrial circle at present, Ca-Co-O base oxide Heat stability is good, can long-term work under high-temperature oxydation atmosphere, has avirulence, pollution-free, Heat stability is good, long service life, preparation simply reach the low advantage of cost, particularly the emphasis that the Ag complex Ca-the Co-O base oxide is studied especially and used.
Because Ag phase skewness in present Ag complex Ca-Co-O base oxide, be prone to agglomeration, and the size of Ag phase particle is generally at 1～3 μ m, cause forming the carrier transport loop at Ca-Co-O base oxide intercrystalline, the Seebeck coefficient (Seebeck coefficient) of Ag complex Ca-Co-O base oxide is significantly reduced, and thermoelectricity capability also significantly reduces thereupon.
The preparation oxide pyroelectric material all needs to obtain earlier precursor powder, obtains the oxide pyroelectric material precursor powder at present and mainly adopts solid phase method; But there is the long (defective of need 10～20h), chemical uniformity is poor, energy consumption reaches oxide pyroelectric material crystal grain big (being 5～10 μ m) greatly of reaction temperature height (reaction temperature is higher than 900 ℃), reaction time in the oxide pyroelectric material precursor powder that adopts the solid phase method preparation.
Summary of the invention
The objective of the invention is in order to solve Ag phase skewness in Ag complex Ca-Co-O base oxide, easily reunite, Ag phase particle size is big, cause forming the carrier transport loop at Ca-Co-O base oxide intercrystalline, make the significantly reduced problem of Seebeck coefficient of Ag complex Ca-Co-O base oxide, and there is the reaction temperature height in the oxide pyroelectric material precursor powder that adopts the solid phase method preparation, the reaction time is long, chemical uniformity is poor, energy consumption reaches the big defective of oxide pyroelectric material crystal grain greatly, and a kind of Ag complex Ca that provides
9Co
12O
28The preparation method of base oxide pyroelectric material.
The Ag complex Ca
9Co
12O
28Base oxide pyroelectric material prepares according to the following steps: one, with Soluble Ca
2+Salt and solubility Co
2+Salt is dissolved in the distilled water by 3: 3.92～4 mol ratio; Two, in step 1 institute obtain solution, add complexing agent citric acid, Ca in the addition of citric acid and the step 1 institute obtain solution
2+And Co
2+The mol ratio of total amount is 1～4: 1; Three, in the mixed solution of step 2, add silver nitrate, the Ca that adds in silver nitrate and the step 1
2+Mol ratio be 0.1～0.3: 3; Four, in the mixed solution of step 3, add acrylamide monomer and N, N '-methylene-bisacrylamide, add acrylamide monomer and N, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 50～100g/L, N, the addition of N '-methylene-bisacrylamide is 1/10～1/4 of an acrylamide monomer quality; Five, heat temperature raising to 70～90 ℃ add the initator azodiisobutyronitrile then and stir, and form gel behind 1～15min, and the addition of azodiisobutyronitrile is 0.3%～1% of an acrylamide monomer quality; Six, moisture is removed in heating using microwave, obtains xerogel; Seven, xerogel is calcined 2～4h under 700～750 ℃ condition, obtains the Ag complex Ca
9Co
12O
28Based oxide powder; Eight, discharge plasma sintering: with the Ag complex Ca
9Co
12O
28Based oxide powder is put into mould, sintering atmosphere be vacuum, powder to bear pressure be that 30～100MPa, temperature are sintering 3～8min under 700～780 ℃ the condition, promptly obtain the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.
Ag complex Ca-Co-O base oxide (the Ag complex Ca of the inventive method preparation
9Co
12O
28) in Ag be evenly distributed the Ag complex Ca mutually
9Co
12O
28Ag phase particle grain size is less than 500nm, at Ca in the base oxide pyroelectric material
9Co
12O
28Intercrystalline does not form the carrier transport loop.The Ag complex Ca of the inventive method preparation
9Co
12O
28Base oxide pyroelectric material compares Ca
9Co
12O
28The Seebeck coefficient improved 2.7%～7.1%, electrical conductivity has improved 21.1%～42.1%, power factor has improved 27.8%～63.0%.
The inventive method is at the Ag complex Ca
9Co
12O
28Do not need to consume expensive organic acid and alcohol in the process of base oxide pyroelectric material precursor powder, cost is lower more than 30% than adopting sol-gel process.
Various ions carry out the even mixing of atom level level in the inventive method in the aqueous solution, and are simple to operate, reaction temperature is low, energy consumption is low, save time (2.5～5 hours whole process of preparation times spent), and can control the Ag complex Ca
9Co
12O
28The chemistry of each element ratio in the base oxide pyroelectric material is saved cost.The Ag complex Ca of the inventive method preparation
9Co
12O
28Base oxide pyroelectric material precursor powder purity is up to more than 95%, and the single synthetic quantity is higher than 100 grams, the prepared Ag complex Ca that goes out
9Co
12O
28The crystallite dimension of base oxide pyroelectric material is 0.5～2 μ m, can satisfy the demand of suitability for industrialized production.
Adopt discharge plasma sintering technique (SPS) can solve the unsound problem of material sintering in the inventive method, and have the advantage that programming rate is fast, sintering time is short, sintering temperature is low, and can guarantee that Ag phase particle grain size is less than 500nm.
Description of drawings
Fig. 1 is the Ca of the specific embodiment 15 preparations
9Co
12O
28The fracture electron scanning figure of-0.3Ag composite ceramics.
The specific embodiment
The specific embodiment one: present embodiment Ag complex Ca
9Co
12O
28Base oxide pyroelectric material prepares according to the following steps: one, with Soluble Ca
2+Salt and solubility Co
2+Salt is dissolved in the distilled water by 3: 3.92～4 mol ratio; Two, in step 1 institute obtain solution, add complexing agent citric acid, Ca in the addition of citric acid and the step 1 institute obtain solution
2+And Co
2+The mol ratio of total amount is 1～4: 1; Three, in the mixed solution of step 2, add silver nitrate, the Ca that adds in silver nitrate and the step 1
2+Mol ratio be 0.1～0.3: 3; Four, in the mixed solution of step 3, add acrylamide monomer and N, N '-methylene-bisacrylamide, add acrylamide monomer and N, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 50～100g/L, N, the addition of N '-methylene-bisacrylamide is 1/10～1/4 of an acrylamide monomer quality; Five, heat temperature raising to 70～90 ℃ add the initator azodiisobutyronitrile then and stir, and form gel behind 1～15min, and the addition of azodiisobutyronitrile is 0.3%～1% of an acrylamide monomer quality; Six, moisture is removed in heating using microwave, obtains xerogel; Seven, xerogel is calcined 2～4h under 700～750 ℃ condition, obtains the Ag complex Ca
9Co
12O
28Based oxide powder; Eight, discharge plasma sintering: with the Ag complex Ca
9Co
12O
28Based oxide powder is put into mould, sintering atmosphere be vacuum, powder to bear pressure be that 30～100MPa, temperature are sintering 3～8min under 700～780 ℃ the condition, promptly obtain the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.
The present embodiment method has that aggregate velocity is fast, reaction temperature is low, chemical uniformity is good, uniform crystal particles, Ag particle grain size distribution narrow (100nm～480nm), with low cost, advantage of high production efficiency, and Ag complex Ca
9Co
12O
28The thermoelectricity capability of base oxide pyroelectric material significantly improves, and can be used for used heat utilization and high temperature power field.
The present embodiment method has been avoided the long-time sintering of high temperature to Ag complex Ca-Co-O base oxide, so effectively control Ag phase particle grain size less than 500nm, has avoided the appearance of Ag phase agglomeration.
Utilize acrylamide Raolical polymerizable and N in the present embodiment method, the difunctional effect of N '-two activity double keys of methylene-bisacrylamide obtains gel thereby macromolecular chain is linked up the formation three-dimensional network.Because the macromolecule network that forms in gel process has stoped the mass transport process in the calcination process, thereby has reduced reunion and grain growth, can effectively control the diameter of particle size.
The various ions of present embodiment method carry out the even mixing of atom level level in the aqueous solution, guaranteed the even distribution of each phase.
Present embodiment method sintering temperature is low only to be 700～780 ℃, and the sintering time weak point is 3～8min.
Present embodiment has been used the carrying out of complexing of metal ion agent citric acid accelerated reaction.Ca
2+And Co
2+Ion easily and monomer acrylamide and N, N '-methylene-bisacrylamide takes place crosslinked, and the effect that resistance gathers is played in the radical polymerization of acrylamide, when GOLD FROM PLATING SOLUTION belongs to the concentration of ion when higher, can delay gelation rate greatly, influences the quality of gel; And employing complexing agent citric acid, citric acid can be earlier and metal ion form stable complex compound, avoid metal ion and monomer acrylamide and N, N '-methylene-bisacrylamide generation cross-linking reaction, reaction can be carried out in the higher solution of concentration of metal ions, improve productive rate.Ca
2+And Co
2+Form the big molecule of complex compound with the complexing agent citric acid, so Ca
2+And Co
2+Be difficult in the macromolecule network that in the process of microwave drying, is limited in forming moving, can effectively prevent the segregation of composition, make ion reach molecular level and evenly mix.
The specific embodiment two: the difference of the present embodiment and the specific embodiment one is: Soluble Ca in the step 1
2+Salt is Ca (NO
3)
24H
2O or Ca (CH
3COO)
2H
2O.Other step and parameter are identical with embodiment one.
The specific embodiment three: the difference of the present embodiment and the specific embodiment one is: solubility Co in the step 1
2+Salt is Co (NO
3)
26H
2O or Co (CH
3COO)
24H
2O.Other step and parameter are identical with embodiment one.
The specific embodiment four: the difference of the present embodiment and the specific embodiment one is: the frequency of heating using microwave is that 2.45GHz, power are 600～800W in the step 6, and microwave heating time is 10～30min.Other step and parameter are identical with embodiment one.
The specific embodiment five: the difference of the present embodiment and the specific embodiment one is: mould is a graphite jig in the step 8.Other step and parameter are identical with embodiment one.
The specific embodiment six: the difference of the present embodiment and the specific embodiment one is: Ca in the addition of citric acid and the step 1 institute obtain solution in the step 2
2+And Co
2+The mol ratio of total amount is 1.5～3.5: 1.Other step and parameter are identical with embodiment one.
The specific embodiment seven: the difference of the present embodiment and the specific embodiment one is: Ca in the addition of citric acid and the step 1 institute obtain solution in the step 2
2+And Co
2+The mol ratio of total amount is 2～3: 1.Other step and parameter are identical with embodiment one.
The specific embodiment eight: the difference of the present embodiment and the specific embodiment one is: Ca in the addition of citric acid and the step 1 institute obtain solution in the step 2
2+And Co
2+The mol ratio of total amount is 2: 1.Other step and parameter are identical with embodiment one.
The specific embodiment nine: the difference of the present embodiment and the specific embodiment one is: add acrylamide monomer and N in the step 4, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 60～90g/L.Other step and parameter are identical with embodiment one.
The specific embodiment ten: the difference of the present embodiment and the specific embodiment one is: add acrylamide monomer and N in the step 4, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 70～80g/L.Other step and parameter are identical with embodiment one.
The specific embodiment 11: the difference of the present embodiment and the specific embodiment one is: N, the addition of N '-methylene-bisacrylamide is 1/9～1/5 of an acrylamide monomer quality.Other step and parameter are identical with embodiment one.
The specific embodiment 12: the difference of the present embodiment and the specific embodiment one is: N, the addition of N '-methylene-bisacrylamide is 1/8～1/6 of an acrylamide monomer quality.Other step and parameter are identical with embodiment one.
The specific embodiment 13: the difference of the present embodiment and the specific embodiment one is: xerogel is calcined 2h down at 750 ℃ in the step 7, gets the Ag complex Ca
9Co
12O
28Based oxide powder.Other step and parameter are identical with embodiment one.
The specific embodiment 14: the difference of the present embodiment and the specific embodiment one is: in the step 8 750 ℃, sintering 5min obtains the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.Other step and parameter are identical with embodiment one.
The specific embodiment 15: present embodiment Ag complex Ca
9Co
12O
28Base oxide pyroelectric material prepares according to the following steps: one, with Ca (NO
3)
24H
2O and Co (NO
3)
26H
2O is dissolved in the distilled water by 3: 3.95 mol ratio; Two, in step 1 institute obtain solution, add complexing agent citric acid, Ca in the addition of citric acid and the step 1 institute obtain solution
2+And Co
2+The mol ratio of total amount is 2: 1; Three, in the mixed solution of step 2, add silver nitrate, the Ca that adds in silver nitrate and the step 1
2+Mol ratio be 0.3: 3; Four, in the mixed solution of step 3, add acrylamide monomer and N, N '-methylene-bisacrylamide, add acrylamide monomer and N, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 60g/L, N, the addition of N '-methylene-bisacrylamide is 1/6 of an acrylamide monomer quality; Five, heat temperature raising to 80 ℃ adds the initator azodiisobutyronitrile then and stirs, and keeps forming gel behind temperature 3～10min of 80 ℃ again, and the addition of azodiisobutyronitrile is 0.5% of an acrylamide monomer quality; Six, moisture is removed in heating using microwave, obtains xerogel; Seven, xerogel is calcined 2h under 720 ℃ condition, obtains the Ag complex Ca
9Co
12O
28Based oxide powder; Eight, discharge plasma sintering: with the Ag complex Ca
9Co
12O
28Based oxide powder is put into graphite jig, sintering atmosphere be vacuum, powder to bear pressure be that 50MPa, temperature are sintering 5min under 750 ℃ the condition, promptly obtain the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.
Fig. 1 is the Ag complex Ca of present embodiment preparation
9Co
12O
28Base oxide pyroelectric material (Ca
9Co
12O
28-0.3Ag composite ceramics) fracture electron scanning figure, as can be seen from Figure 1 the Ag complex Ca of present embodiment preparation
9Co
12O
28Base oxide pyroelectric material (Ca
9Co
12O
28-0.3Ag composite ceramics) density height, pore-free, Ca
9Co
12O
28Crystal grain is the synusia shape, and crystallite dimension is 1～2 μ m, analyzes through power spectrum (EDX), and arrow indication white bright spot is rich Ag phase among Fig. 1, and Ag is evenly distributed mutually, and Ag phase particle grain size is less than 500nm.
The specific embodiment 16: the difference of the present embodiment and the specific embodiment 13 is: the silver nitrate that adds in the step 3 is divided into three groups, respectively with step 1 in the Ca that adds
2+Mol ratio be 0.1: 3,0.2: 3 and 0.3: 3.Other step and parameter are identical with embodiment 13.
The Ag complex Ca that present embodiment is prepared
9Co
12O
28Base oxide pyroelectric material has only Ca through the XRD spectra analysis
9Co
12O
28Principal crystalline phase and Ag existence mutually do not have other assorted peak.
3 groups of Ag complex Cas that present embodiment is prepared
9Co
12O
28Base oxide pyroelectric material (is respectively Ca
9Co
12O
28-0.1Ag composite ceramics, Ca
9Co
12O
28-0.2Ag composite ceramics and Ca
9Co
12O
28-0.3Ag composite ceramics) and Ca
9Co
12O
28Under 700 ℃ of conditions, test thermoelectricity capability, 3 groups of Ag complex Cas
9Co
12O
28The thermoelectricity capability of base oxide pyroelectric material is as shown in table 1.
Ag complex Ca under 700 ℃ of conditions of table 1
9Co
12O
28The thermoelectricity capability of base oxide pyroelectric material
| Sample | Seebeck coefficient μ V/K | Electrical conductivity S/cm | Power factor 10 -4Wm -1K -2 |
| Ca 9Co 12O 28-0.3Ag | 195 | 162 | 6.16 |
| Ca 9Co 12O 28-0.2Ag | 192 | 155 | 5.71 |
| Ca 9Co 12O 28-0.1Ag | 187 | 138 | 4.83 |
| Ca 9Co 12O 28 | 182 | 114 | 3.78 |
Test data shows, the Ag complex Ca that present embodiment is prepared
9Co
12O
28The Seebeck coefficient ratio Ca of base oxide pyroelectric material
9Co
12O
28Base oxide has improved 2.7%～7.1%, and electrical conductivity has improved 21.1%～42.1%, and power factor has improved 27.8%～63.0%, and thermoelectricity capability is significantly improved.
Claims (9)
1. Ag complex Ca
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material prepares according to the following steps: one, with Soluble Ca
2+Salt and solubility Co
2+Salt is dissolved in the distilled water by 3: 3.92～4 mol ratio; Two, in step 1 institute obtain solution, add complexing agent citric acid, Ca in the addition of citric acid and the step 1 institute obtain solution
2+And Co
2+The mol ratio of total amount is 1～4: 1; Three, in the mixed solution of step 2, add silver nitrate, the Ca that adds in silver nitrate and the step 1
2+Mol ratio be 0.1～0.3: 3; Four, in the mixed solution of step 3, add acrylamide monomer and N, N '-methylene-bisacrylamide, add acrylamide monomer and N, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 50～100g/L, N, the addition of N '-methylene-bisacrylamide is 1/10～1/4 of an acrylamide monomer quality; Five, heat temperature raising to 70～90 ℃ add the initator azodiisobutyronitrile then and stir, and form gel behind 1～15min, and the addition of azodiisobutyronitrile is 0.3%～1% of an acrylamide monomer quality; Six, moisture is removed in heating using microwave, obtains xerogel; Seven, xerogel is calcined 2～4h under 700～750 ℃ condition, obtains the Ag complex Ca
9Co
12O
28Based oxide powder; Eight, discharge plasma sintering: with the Ag complex Ca
9Co
12O
28Based oxide powder is put into mould, sintering atmosphere be vacuum, powder to bear pressure be that 30～100MPa, temperature are sintering 3～8min under 700～780 ℃ the condition, promptly obtain the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.
2. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that Soluble Ca in the step 1
2+Salt is Ca (NO
3)
24H
2O or Ca (CH
3COO)
2H
2O.
3. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that solubility Co in the step 1
2+Salt is Co (NO
3)
26H
2O or Co (CH
3COO)
24H
2O.
4. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material, the frequency that it is characterized in that heating using microwave in the step 6 are that 2.45GHz, power are 600～800W, and microwave heating time is 10～30min.
5. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that mould is a graphite jig in the step 8.
6. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that Ca in the addition of citric acid in the step 2 and the step 1 institute obtain solution
2+And Co
2+The mol ratio of total amount is 2: 1.
7. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that in the step 4 adding acrylamide monomer and N, behind N '-methylene-bisacrylamide in the mixed solution concentration of acrylamide monomer be 60～90g/L.
8. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that xerogel is calcined 2h down at 750 ℃ in the step 7, gets the Ag complex Ca
9Co
12O
28Based oxide powder.
9. a kind of Ag complex Ca according to claim 1
9Co
12O
28The preparation method of base oxide pyroelectric material is characterized in that in the step 8 750 ℃, and sintering 5min obtains the Ag complex Ca
9Co
12O
28Base oxide pyroelectric material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817092A (en) * | 2010-04-02 | 2010-09-01 | 北京科技大学 | Method for preparing pre-alloyed powder for nanometer-level dispersion-strengthened metal |
| CN104679965A (en) * | 2015-03-25 | 2015-06-03 | 湖北工业大学 | Method for forecasting thermoelectric conversion power factors of bismuth telluride through WIEN2K software |
| CN108950347A (en) * | 2018-07-02 | 2018-12-07 | 华中科技大学 | A kind of preparation method of MgAgSb pyroelectric material |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
| CN115894024A (en) * | 2022-09-27 | 2023-04-04 | 清华大学 | LaAgSeO thermoelectric material and preparation method and application thereof |
-
2007
- 2007-11-21 CN CNB2007101446429A patent/CN100528428C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817092A (en) * | 2010-04-02 | 2010-09-01 | 北京科技大学 | Method for preparing pre-alloyed powder for nanometer-level dispersion-strengthened metal |
| CN104679965A (en) * | 2015-03-25 | 2015-06-03 | 湖北工业大学 | Method for forecasting thermoelectric conversion power factors of bismuth telluride through WIEN2K software |
| CN108950347A (en) * | 2018-07-02 | 2018-12-07 | 华中科技大学 | A kind of preparation method of MgAgSb pyroelectric material |
| CN109616678A (en) * | 2018-12-03 | 2019-04-12 | 华中科技大学 | A kind of high Seebeck coefficient water system heat chemistry battery and device |
| CN109616678B (en) * | 2018-12-03 | 2020-10-02 | 华中科技大学 | high-Seebeck-coefficient water-based thermochemical battery and device |
| CN115894024A (en) * | 2022-09-27 | 2023-04-04 | 清华大学 | LaAgSeO thermoelectric material and preparation method and application thereof |
| CN115894024B (en) * | 2022-09-27 | 2023-11-21 | 清华大学 | LaAgSeO thermoelectric material and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100528428C (en) | 2009-08-19 |
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