CN109716546A - Thermoelectric conversion layer forms the manufacturing method for using composition and thermoelectric conversion layer - Google Patents
Thermoelectric conversion layer forms the manufacturing method for using composition and thermoelectric conversion layer Download PDFInfo
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- CN109716546A CN109716546A CN201780057189.XA CN201780057189A CN109716546A CN 109716546 A CN109716546 A CN 109716546A CN 201780057189 A CN201780057189 A CN 201780057189A CN 109716546 A CN109716546 A CN 109716546A
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
-
- 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
- H10N10/856—Thermoelectric active materials comprising organic compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Mention the thermoelectric conversion layer formation composition to water as decentralized medium.In addition, manufacturing thermoelectric conversion layer using coated technique using thermoelectric conversion layer formation composition.A kind of thermoelectric conversion layer formation composition, include (A) water, (B) cobalt system's oxide and (C) polysaccharide, relative to 100 mass parts of the composition, (A) water and (B) cobalt system oxide add up to 90~99.98 mass parts, (B) cobalt system oxide is 1~50 mass parts, and (C) polysaccharide is 0.02~10 mass parts.
Description
Technical field
The present invention relates to the thermoelectric conversion layer formation composition for being used to form thermoelectric conversion layer and thermoelectricity is used to turn
Change the manufacturing method of the thermoelectric conversion layer of layer formation composition.
Background technique
Due to the temperature between the high-temperature portion and low temperature portion of the electromotive force and thermoelectric conversion element that are generated by Seebeck effect
Difference is proportional, so being turned mostly using the thermoelectricity of block shape in previous thermo-electric conversion module to significantly obtain temperature difference
Change element.But the thermoelectric conversion element of block shape is asked in the presence of what the power generation unit price for being not easy progress microfabrication, module was got higher
Topic.Therefore, the thermoelectric conversion element for having used coated technique and heat to electricity conversion mould of easy microfabrication are reported in recent years
The research of block.Wherein, it from the viewpoint of environmental protection, consumingly expects and turns water as the thermoelectricity of main decentralized medium
Change the exploitation of layer formation composition.
As the thermoelectric conversion layer of the coated technique formation by using water, Patent Document 1 discloses use packet
Water system composition containing semiconductive particles and electroconductive polymer forms the scheme of envelope on supporting mass.In addition, in patent text
It offers and is disclosed in 2 by manufacturing heat to electricity conversion piece comprising metal nanoparticle and the high molecular water system composition of water-soluble conducting
Technology.Patent Document 3 discloses make conjugated system electroconductive polymer be dissolved in the water flexible heat to electricity conversion is made
Layer.On the other hand, Patent Document 4 discloses the heat to electricity conversion for using α-terpineol as solvent and making cobalt system oxide
Layer.
Citation
Patent document
Patent document 1:WO2013/141065 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-30010 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2014-199838 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2008-270410 bulletin
Summary of the invention
1~patent document of patent document 3 is turned using thermoelectricity made of thermo-electric converting material is dispersed or dissolved in water
Layer formation composition is changed, the technology of thermoelectric conversion layer has been made of coated technique.But these prior arts used it is resistance to
Hot low thermo-electric converting material, the not heat resistance in high temperature region (300~600 DEG C).
Patent document 4 has used organic solvent to make thermoelectric conversion layer.So far, for high temperature region
Thermoelectric conversion layer does not take water as a solvent the example of the thermoelectric conversion layer formation composition of decentralized medium.
The subject of the invention is to provide the high temperature regions that can be applied to 300~600 DEG C using water as decentralized medium
Composition is used in thermoelectric conversion layer formation.In addition, project of the invention is to pass through coating using thermoelectric conversion layer formation composition
Technique manufactures thermoelectric conversion layer.
The present inventor is concentrated on studies in order to solve above-mentioned problem, as a result, it has been found that including (A) water, (B) cobalt system
The thermoelectric conversion layer formation of oxide and (C) polysaccharide composition has good dispersibility and screening characteristics, in addition,
It was found that by under oxidizing atmosphere by polysaccharide contained in the envelope made of thermoelectric conversion layer formation composition
It is burnt into, the thermoelectric conversion layer excellent there is no the pyroelecthc properties for the ingredient for hindering pyroelecthc properties can be manufactured, to complete
The present invention.
That is, in the present invention, as the first viewpoint, being related to a kind of thermoelectric conversion layer formation composition, it includes (A)
Water, (B) cobalt system's oxide and (C) polysaccharide, relative to 100 mass parts of the composition, the conjunction of (A) water and (B) cobalt system oxide
90~99.98 mass parts are calculated as, (B) cobalt system's oxide is 1~50 mass parts, and (C) polysaccharide is 0.02~10 mass parts.
It is the thermoelectric conversion layer formation composition according to the first viewpoint as the second viewpoint, the polysaccharide is
Cellulose derivative.
It is the thermoelectric conversion layer formation composition according to the second viewpoint as third viewpoint, the cellulose spreads out
Biology is hydroxypropyl methyl cellulose.
It is that the thermoelectric conversion layer according to the first viewpoint~third viewpoint any viewpoint forms use as the 4th viewpoint
Composition, cobalt system oxide are the compounds indicated with following general formulas (1), general formula (2) or general formula (3),
Caa1A1 b1Coc1A2 d1Oe1 (1)
In formula (1), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanum
Series elements at least one of element, A2It is to be selected among Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least
A kind of element, 2.2≤a1≤3.6,0≤b1≤0.8,2.0≤c1≤4.5,0≤d1≤2.0,8≤e1≤10；
Naa2A1 b2Coc2A2 d2Oe2 (2)
In formula (2), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanum
Series elements at least one of element, A2It is to be selected among Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least
A kind of element, the 0 < < of a2≤2,0≤b2≤0.6,0 c2≤2,0≤d2≤0.6,1.0≤e2≤3.0；
Bia3M1 f3A1 b3Coc3A2 d3Oe3 (3)
In formula (3), M1It is Sr or Pb, A1Be selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba,
Al, Bi, Y and lanthanide series at least one of element, A2Be selected from Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and
Ta at least one of element, 1.8≤a3≤2.2,0≤f3≤0.4,1.8≤b3≤2.2,1.6≤c3≤2.2,0≤d3
≤ 0.5,8≤e3≤10.
As the 5th viewpoint, be related to a kind of manufacturing method of thermoelectric conversion layer comprising: to the 1st viewpoint of coating of substrates~
The process that thermoelectric conversion layer formation described in any viewpoint of 4th viewpoint forms envelope with composition；Then in order to from this
Envelope removes polysaccharide and the process of being burnt into the envelope in 300 DEG C or more of oxidizing atmosphere.
As the 6th viewpoint, it is related to a kind of manufacturing method of thermoelectric conversion layer comprising: to the 1st viewpoint~4 of coating of substrates
The process that thermoelectric conversion layer formation described in any viewpoint of viewpoint forms envelope with composition；Then in order to from the envelope
The process for removing polysaccharide and the envelope being subjected to light firing by light irradiation in oxidizing atmosphere.
As the 7th viewpoint, it is related to a kind of manufacturing method of thermoelectric conversion layer comprising: to the 1st viewpoint~4 of coating of substrates
The process that thermoelectric conversion layer formation described in any viewpoint of viewpoint forms envelope with composition；It is more in order to be removed from the envelope
Carbohydrate and the process for being burnt into the envelope in 300 DEG C or more of oxidizing atmosphere；With so by the envelope in oxidizing atmosphere
In light firing is carried out by light irradiation process.
In the present invention, due to using water as main solvent, so the heat that the pollution for being capable of providing environment and operating environment is few
Composition is used in electric conversion layer formation.In addition, being capable of providing by using the composition with heat-resisting in high temperature region
Property, pyroelecthc properties it is excellent and with processability and freedom shape thermoelectric conversion layer.
Detailed description of the invention
Fig. 1 is the surface shape of thermoelectric conversion layer A1 and the scanning electron microscope observation image of cross sectional shape.
Fig. 2 (a) is that (is the diffraction of aluminum oxide substrate for the X-ray diffractogram of the embodiment layer A2 on aluminum oxide substrate
Peak), Fig. 2 (b) is the Ca used in the feed3Co4O9X-ray diffractogram (the Ca of powder3Co4O9It is expressed as in Fig. 2
Co349。)。
Specific embodiment
Hereinafter, being described in detail to the present invention.Thermoelectric conversion layer formation of the invention is by base with composition
Plate applies and carries out the composition that firing is capable of forming the thermoelectric conversion layer formed by cobalt system oxide.That is, in the group
Close the state dispersion that the cobalt system oxide of thermoelectric conversion layer is used to form in object with particle, water and polysaccharide contained in the composition
Class is the ingredient for improving the dispersity of cobalt system oxide.
The fundamental characteristics of thermoelectric conversion layer is aoxidized by the cobalt system dispersed in the thermoelectric conversion layer formation composition
The type of object determines.That is, the cobalt system oxide dispersed in thermoelectric conversion layer formation composition of the invention, as long as
It can disperse in water, it will be able to use the thermo-electric converting material formed by known cobalt system oxide as former state.From another sight
From the point of view of point, it may also be said to it in the cobalt system oxide that the Seebeck coefficient at 100 DEG C is 50 μ V/K or more is thermo-electric converting material,
These known cobalt system oxides are able to use in the present invention as starting material.
Furthermore polysaccharide be when thermoelectric conversion layer formation composition of the invention is formed as thermoelectric conversion layer in order to
The particle of cobalt system oxide is bonded to each other and is added.By adding polysaccharide, in the film forming procedure of thermoelectric conversion layer, institute
It states after thermoelectric conversion layer formation is dried with composition, particle will not be peeled off from substrate, can be used as thermoelectric conversion layer
It is present on substrate.On the other hand, in the case where not including polysaccharide, when being combined the drying of object, cobalt system oxide
Particle can easily be peeled off from substrate, cannot function as thermoelectric conversion layer and exist.
When polysaccharide includes more, it is possible to the resistive penalties of thermoelectric conversion layer, but by 300 DEG C or more of high temperature
Under be burnt into decompose, good electric conductivity can be obtained.Although polysaccharide is not present in the thermoelectric conversion layer after firing,
But it is weaker fused, can be existed as layer each other by cobalt system oxide.Furthermore polysaccharide, which also has, improves the oxidation of cobalt system
The effect of the dispersibility of object particle in water.
In addition, the thermoelectric conversion layer of the cobalt system oxide obtained using thermoelectric conversion layer formation of the invention with composition,
Its crystallinity is simultaneously not limited.As thermoelectric conversion layer, good characteristic, preferably crystal in order to obtain, for example, even if starting
Raw material is amorphous, is burnt by and to after coating of substrates thermoelectric conversion layer formation composition in order to crystallize,
It can obtain the thermoelectric conversion layer of superperformance.
In addition, the starting material as cobalt system oxide, manufactured even being included in it for example in cobalt system oxide
In journey the case where remaining carbon component, as long as carbon component can be decomposed by being burnt into, it will be able to it is good to obtain pyroelecthc properties
Thermoelectric conversion layer.
In addition, similarly, the oxygen atom of cobalt system oxide can also import in firing process after coating, therefore also can
Cobalt system oxide enough fewer than stoichiometric ratio using the content of oxygen atom.
As long as that is, to after coating of substrates thermoelectric conversion layer formation composition of the invention, by appropriate
Firing processing, can obtain sufficient characteristic as thermoelectric conversion layer, then can not also as the cobalt system oxide of starting material
With sufficient heat to electricity conversion characteristic.
Such cobalt system oxide is indicated with following general formulas (1), (2) or (3).
General formula (1):
Caa1A1 b1Coc1A2 d1Oe1 (1)
In formula (1), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanum
Series elements at least one of element, A2It is to be selected among Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least
A kind of element, 2.2≤a1≤3.6,0≤b1≤0.8,2.0≤c1≤4.5,0≤d1≤2.0,8≤e1≤10.
The particularly preferred cobalt system oxide indicated with general formula (1) is shown in table 1.
Table 1
| Composition formula | A1 | A2 | a1 | b1 | C1 | d1 | e1 |
| Ca3Co4O9 | - | - | 3 | 0 | 4 | 0 | 9 |
| Ca2.7Bi0.3Co4O9 | Bi | - | 2.7 | 0.3 | 4 | 0 | 9 |
| Ca2.7Sr0.3Co4O9 | Sr | - | 2.7 | 0.3 | 4 | 0 | 9 |
In above-mentioned general formula (1), as lanthanide series, can illustrate La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm,
Yb, Lu etc..
General formula (2):
Naa2A1 b2Coc2A2 d2Oe2 (2)
In formula (2), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanum
Series elements at least one of element, A2It is to be selected among Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least
A kind of element, the 0 < < of a2≤2,0≤b2≤0.6,0 c2≤2,0≤d2≤0.6,1.0≤e2≤3.0.
General formula (3):
Bia3M1 f3A1 b3Coc3A2 d3Oe3 (3)
In formula (3), M1It is Sr or Pb, A1Be selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba,
Al, Bi, Y and lanthanide series at least one of element, A2Be selected from Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and
Ta at least one of element, 1.8≤a3≤2.2,0≤f3≤0.4,1.8≤b3≤2.2,1.6≤c3≤2.2,0≤d3
≤ 0.5,8≤e3≤10.
In the present invention, in order to be dispersed in water cobalt system oxide, cobalt system oxide needs for particle shape.If cobalt system
The average grain diameter of oxide is 1nm or more and 100 μm hereinafter, then can easily prepare uniform dispersion liquid.When for 1nm or less
When, particle aggregates with one another and is difficult to disperse, and when for 100 μm or more, not only dispersibility is deteriorated, but also uniform in the presence of that cannot be formed
Thermoelectric conversion layer the problem of.Furthermore from the screening characteristics of dispersion liquid, the viewpoints such as pyroelecthc properties of thermoelectric conversion layer, this is flat
Equal partial size is preferably 5 μm hereinafter, more preferably 1 μm or less.Here, average grain diameter refers to using Microtrac BEL's
Nanotrac UPA-EX, the partial size gone out using dynamic light scattering determination.
As starting material when preparing thermoelectric conversion layer formation composition of the invention, the average grain of cobalt system oxide
Diameter is not particularly limited as long as 1nm or more.Even if the partial size of starting material is 100 μm or more, by adopting after mixing with water
Particle is crushed with case of wet attrition, can also obtain the cobalt system oxide for the partial size that can be dispersed in water.
Polysaccharide refers to through glycosidic bond, the general name for the substance that monosaccharide molecules more than 2 molecules is polymerized.As
Polysaccharide used in the present invention, preferred cellulose, starch, amylose (amylose), amylopectin (amylopectin),
Glycogen (glycogen), chitin (chitin), agarose, carrageenan (carrageenan), heparin, hyaluronic acid, fruit
Glue, xyloglucan (xyloglucan) etc..
Polysaccharide is to turn for the dispersibility of improvement cobalt system oxide and the purpose of screening characteristics in thermoelectricity of the invention
Layer formation is changed with adding in composition.In the composition, polysaccharide exists with the state for dissolving or being dispersed in water.
Among polysaccharide, about cellulose, it is known that derivative made of many partial modifications, for example, as it is known that carboxylic
Methylcellulose, hydroxyethyl cellulose, hydroxyethylmethylcellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl are fine
Tie up element, ethyl cellulose, ethylhydroxyethylcellulose, carboxymethylethylcellulose, NC Nitroncellulose, cellulose acetate etc..From
When forming thermoelectric conversion layer, the angle for being capable of forming the thermoelectric conversion layer that film forming is good and volume resistivity is small is set out, excellent
Methylcellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyethylmethylcellulose, hydroxyethyl cellulose are selected, it is more excellent
Select hydroxypropyl methyl cellulose.
Relative to thermoelectric conversion layer formation of the invention 100 mass parts of composition, the additive amount of polysaccharide is 0.02~
10 mass parts.Polysaccharide is more added, the mutual cementability of particle of cobalt system oxide is the better, and film forming is better
It is good.On the other hand, thermoelectric conversion layer with good conductivity in order to obtain needs to make remaining polysaccharide in thermoelectric conversion layer point
Solution, from this viewpoint, polysaccharide are few preferably.According to above-mentioned reason, the additive amount of polysaccharide is preferably 0.04~5 mass
Part, more preferably 0.1~2.5 mass parts.
Thermoelectric conversion layer formation water contained in composition institute of the invention, has as dividing cobalt system oxide
The function of scattered decentralized medium.By the way that, comprising water, cobalt system oxide is uniformly dispersed in thermoelectric conversion layer formation composition,
It is capable of forming uniform thermoelectric conversion layer.
In addition, in the present invention, from the viewpoint of the protection of environment and operating environment, using water as main point
Dispersion media.Accordingly, with respect to thermoelectric conversion layer formation of the invention 100 mass parts of composition, (A) water and (B) cobalt system are needed
Oxide adds up to 90 mass parts or more, more than preferably 95 mass parts.
Thermoelectric conversion layer of the invention, which is formed, uses composition, can be added with free from environmental pollution and operating environment range
Hydrophilic solvent.Hydrophilic solvent can be previously added in water as decentralized medium.Hydrophilic solvent is sent out primarily for inhibition
The purpose of bubble and improves the purpose of film forming and add.Specifically, methanol, ethyl alcohol, 1- propyl alcohol, 2- third can be used compatibly
Alcohol, n-butyl alcohol, 2- butanol, acetonitrile.
Relative to the thermoelectric conversion layer formation 100 mass parts of composition, from the sight of the protection of environment and operating environment
Point sets out, and the decentralized medium other than water is preferably that 9.98 below the mass, more preferably 5 below the mass.
In thermoelectric conversion layer formation composition of the invention, (B) cobalt system's oxide and (C) polysaccharide as solid at
Divide and exists.When the solid component concentration of composition is excessively high, the composition does not have mobility, cannot be easy using coating process
Ground obtains thermoelectric conversion layer.On the other hand, when solid component concentration is too low, the composition cannot obtain uniform film.Therefore,
Relative to 100 mass parts of the composition, add up to 1.02~60 mass parts of (B) the cobalt system's oxide with (C) polysaccharide are needed, it is excellent
It is selected as 10~30 mass parts, more preferably 15~25 mass parts.
The preparation method of thermoelectric conversion layer formation composition of the invention is not particularly limited.Respectively into reaction vessel
It appropriately adding raw materials and mixes, carries out case of wet attrition as needed, thermoelectric conversion layer of the invention can be obtained and formed with combination
Object.As preparation example, for example, water and cellulose derivative are added into container, be stirred to cellulose derivative be completely dissolved for
Only.Then, cobalt system oxide is added in Xiang Tongyi container.As needed, 1- propyl alcohol is added in order to inhibit to foam.In turn, it is
So that it equably mixed, dispersed, by used the ball-milling treatment of zirconium oxide bead, thermoelectric conversion layer can be obtained and formed
Use composition.The condition of ball-milling treatment be, for example, on mixing gyrator (revolving speed of gyrator be 100rpm) processing 5 days or
Sand mill (revolving speed 500rpm) is used to handle 4 hours.Zirconium oxide bead is that 1mm net below is filtered by using mesh,
It can easily be removed from the composition.
Thermoelectric conversion layer of the invention, which is formed, uses composition, by dripping the composition to substrate, forms the composition
Envelope after, keep decentralized medium dry, so as to form the thermoelectric conversion layer being made of cobalt system oxide.But in the shape
Under state, there are polysaccharides between the particle of cobalt system oxide, therefore become the excessively poor thermoelectric conversion layer of electric conductivity.In order to obtain
Thermoelectric conversion layer with good conductivity needs further to be burnt at a temperature of polysaccharide is decomposed.About the firing, in oxygen
It is burnt under change atmosphere at 300 DEG C or more appropriate.But when firing temperature is excessively high, the cobalt system oxide with pyroelecthc properties
Phase transformation is carried out, therefore the upper limit of firing temperature is limited by the phase transition temperature of cobalt system oxide.For example, making as cobalt system oxide
Use Ca3Co4O9In the case where, since phase transition temperature is 860 DEG C, firing temperature is preferably 850 DEG C or less.In addition, firing temperature
The upper limit of degree is also limited by the substrate used.For example, firing temperature is preferably using the flexible substrate of resin
450 DEG C or less.On the other hand, if using heat resistance substrate sufficiently high, the ceramic substrate such as aluminium oxide, quartz base plate
Deng, then can 600 DEG C or more at a temperature of be burnt into.
As firing process, other than using the heating of the progress such as baking oven firing, additionally it is possible to used ultraviolet light,
The light of the light irradiation of visible light, flash of light etc. is burnt into (light sintering).In addition, also can and be burnt into heating firing and light.
Light firing, as long as can be at a temperature of polysaccharide decomposes to the quilt obtained by thermoelectric conversion layer formation with composition
Film is burnt into.
As the light source of light irradiation, such as mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp (chemical can be enumerated
Lamp), carbon arc lamp etc..It is irradiated as light, such as can compatibly enumerate that the scan exposure carried out using iraser, xenon puts
The high illumination flash exposure of electric light etc., infrared lamp exposure etc..For example, the irradiation of xenon pulsed light can be enumerated.
It is burnt into, to envelope surface irradiation light and can be heated in a short time by light, therefore is right with heat can be reduced
The advantages of influence of substrate.In addition, light firing also has the advantages that productivity is high due to that can be burnt into a short time.
As substrate, as long as electrical insulating property substrate, is just not particularly limited, quartz base plate, glass substrate, oxidation can be used
The substrate of the resin of ceramic substrate, the polyimides of aluminium etc. etc., metal substrate with insulating layer etc..
The drying of applying device and film and burning apparatus are able to use generally known device.Specifically, can enumerate
Spin coater, narrow slot-coating machines, blade coating, roll coater, ink-jet, dip-coating, silk-screen printing etc..Device used in dry and firing,
Heating plate, baking oven, lamp heating device etc. can be enumerated.In addition, as used device is burnt into, other than heating device, also
Ultraviolet light, visible light, light irradiation device of flash of light etc. can be enumerated.
Embodiment
Hereinafter, enumerating embodiment more specifically to describe the present invention, but the present invention is not limited by description below.Again
Person, in embodiment, device used in analysis of the adjustment of sample with transitivity and condition are as follows.
[device]
(1) electric furnace (Muffle furnace)
Device: hillside plot motor (strain) makes desk-top Muffle furnace Y-2025-N
(2) spin coater
Device: ミ カ サ (strain) spin coater 1H-D7 processed
(3) resistrivity meter (sheet resistance value measurement)
Device: Mitsubishi Chemical's (strain) Loresta GP processed
Probe: Mitsubishi Chemical's (strain) PSP probe processed (probe spacing from: 1.5mm)
(4) scanning electron microscope
Device: Japan Electronics (strain) field emission type scanning electron microscope JSM-7400F processed
(5) film thickness measuring
Device: (strain) small slope studies made fine shape measuring machine サ ー Off U ー ダ ET4000
(6) Wide angle X-ray diffraction
Device: (strain) リ ガ Network society X-ray diffraction device RINT Ultime+
Determination condition:
X-ray source: Cu；Voltage: 40kV；Electric current: 40mA；STEP width: 0.04 °；Cumulative time: 0.5 second/STEP；Hair
Scattered slit: 1 °；The longitudinal limitation slit of diverging: 10mm；Scatter slit: 1 °；By optical slits: 0.3mm.
(7) pyroelecthc properties are evaluated
Device: オ ザ ワ scientific (strain) heats electrical characteristics determining device RZ2001i
Electrode: membrane electrode
(8) grain size analysis meter
Device: Microtrac BEL (strain) Nanotrac processed (registered trademark) UPA-EX
(9) light is burnt into
Device: Xenon society xenon pulsed light sintering equipment S-2210
[raw material]
Cobalt system oxide: Ca3Co4O9
(body in Nanotrac UPA-EX measurement volume particle size distribution processed using Microtrac BEL (strain) is used
The Ca that accumulation meter 50% is 0.46 μm3Co4O9。)
HPMC-1: hydroxypropyl methyl cellulose (SHIN-ETSU HANTOTAI's chemical industry (strain) Metolose processed (registered trademark) 60SH-
03)
HPMC-2: hydroxypropyl methyl cellulose (SHIN-ETSU HANTOTAI's chemical industry (strain) Metolose 60SH-15 processed)
MC: methylcellulose (SHIN-ETSU HANTOTAI's chemical industry (strain) Metolose MC processed)
HEC: hydroxyethyl cellulose (daicelfinechem (strain) HEC Daicel SE400 processed)
PVA: polyvinyl alcohol (Japanese jealous woman ビ ポ バ ー Le (strain) AT-17 processed)
PEG: polyethylene glycol (day oil (strain) PEG#4000 processed)
Normal propyl alcohol (pure chemistry (strain) system)
[embodiment 1]
It is dissolved in the HPMC-1 (0.05g, 1 mass parts) as polysaccharide in water (3.5g, 74 mass parts).It is added to
Ca3Co4O9(1.0g, 20 mass parts) and normal propyl alcohol (0.25g, 5 mass parts).The zirconium oxide bead for further adding φ 1mm, mixed
It closes on gyrator (100rpm) ball-milling treatment 5 days, has obtained example composition A.
[embodiment 2~4]
Other than being set as the composition of table 3, using step same as Example 1, example composition B~D has been obtained.
[comparative example 1]
PVA (0.05g, 1 mass parts) is set to be dissolved in water (3.5g, 74 mass parts).It is added to Ca3Co4O9(1.0g, 20 mass
Part) and normal propyl alcohol (0.25g, 5 mass parts).Further add the zirconium oxide bead of φ 1mm, the ball in mixing gyrator (100rpm)
Mill processing 5 days, has obtained comparative example composition a.
[comparative example 2]
In addition to using PEG (0.05g, 1 mass parts) to come other than substitution for PVA, using the step identical as comparative example 1, obtain
The comparative example composition b of the composition of table 4.
[comparative example 3]
Other than being not added with PVA, using the step identical as comparative example 1, the comparative example combination of the composition of table 4 has been obtained
Object c.
[comparative example 4]
In addition to having used other than HPMC-1 (0.0005g, 0.01 mass parts) as polysaccharide, use is same as Example 1
The step of, obtain the comparative example composition d of the composition of table 4.
[comparative example 5]
In addition to using other than HPMC-1 (0.0001g, 0.002 mass parts) as polysaccharide, use is same as Example 1
The step of, obtain the comparative example composition e of the composition of table 4.
[embodiment 5]
The example composition A for dripping a small amount of on alkali-free glass substrate (25mm × 25mm), uses spin-coating method
(700rpm) forms film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour, obtains at 600 DEG C
Embodiment layer A1.Embodiment layer A1 also can't see crackle, removing after 100 DEG C of drying and after 600 DEG C of firings of film, really
Recognize and equably covers on the glass substrate.The surface state of embodiment layer A1 and the sweep type of section state is shown in FIG. 1
Electron microscope (SEM) observes result.About embodiment layer A1, Ca is able to confirm that by SEM observation3Co4O9Particle stacking to
Form 3.2 μm of layer.
[embodiment 6]
The example composition A for dripping a small amount of on aluminum oxide substrate (10mm × 15mm) is used spin-coating method (700rpm)
Form film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour at 600 DEG C, has obtained embodiment layer
A2.Embodiment layer A2 also can't see crackle, removing after decentralized medium is dry and after film firing, confirm and equably cover
On aluminum oxide substrate.The measurement result of the Wide angle X-ray diffraction of embodiment layer A2 is shown in FIG. 2.(b) raw material in Fig. 2
Powder, (a) film all have Ca3Co4O9Diffraction maximum, be able to confirm that it is the thermoelectric conversion layer being made of cobalt system oxide.
[embodiment 7]
About the Seebeck coefficient of the embodiment layer A2 formed on aluminum oxide substrate obtained in the embodiment 6, pass through
Make the temperature difference for being heated to 0~5 DEG C of generation in the face of 100 DEG C, 350 DEG C or 600 DEG C of embodiment layer A2, and measures and generate at this time
Voltage and calculate.Be shown in table 2 be heated to 100 DEG C, 350 DEG C and 600 DEG C embodiment layer A2 Seebeck coefficient.Energy
Enough confirming embodiment layer A2 has excellent heat to electricity conversion ability the high temperature region at 600 DEG C.
Table 2
[embodiment 8]
The example composition A for dripping a small amount of on alkali-free glass substrate (25mm × 25mm), uses spin-coating method
(700rpm) forms film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour, obtains at 600 DEG C
Embodiment layer A3.Embodiment layer A3 also can't see crackle, removing, confirmation after decentralized medium is dry and after film firing
To equably covering on the glass substrate.In addition, the film thickness of embodiment layer A3 is 4.4 μm, volume resistivity is 148m Ω cm.It is aobvious
Showing example composition A3 is the composition not caused environmental damage, and is capable of forming the good uniform thermoelectricity of characteristic
Conversion layer.
[embodiment 9~13]
Other than being set as the composition of table 3, using step same as Example 1, example composition E~I has been obtained.
[embodiment 14~21]
Other than using example composition B~I, using similarly to Example 8 the step of obtain embodiment layer B1~
I1.Embodiment layer B1~I1 also can't see crackle, removing, confirmation after 100 DEG C of drying and after 600 DEG C of firings of film
To equably covering on the glass substrate.The film thickness and conductivity of embodiment layer B~D is as shown in table 5.Show that embodiment combines
Object B~D is the composition not caused environmental damage, and is capable of forming the good uniform thermoelectric conversion layer of characteristic.
[comparative example 6~10]
Other than using comparative example composition a~e, using similarly to Example 5 the step of come attempt system contrast
Example layer a1~e1, but crackle, removing occur after 100 DEG C of drying for comparative example layer a1~e1, can not be formed on substrate
Thermoelectric conversion layer.About comparative example layer a1, b1, it is believed that due to PVA or PEG and Ca3Co4O9Do not disperse fully and agglomerate,
Therefore resin component can not be utilized Ca3Co4O9Particle is fixed on substrate, and crackle, removing have occurred after the drying.About
Comparative example layer c1~e1, it is believed that since there is no an adequate amount of polysaccharide, so each other or particle is in conjunction with substrate by particle
Ingredient is insufficient, and crackle, removing have occurred after the drying.Confirm: substituting polysaccharide and be added to the composition (ratio of PVA, PEG
The composition (comparative example composition c~e) insufficient compared with the additive amount of composition a, comparative example composition b) and polysaccharide does not have
It is played a role as thermoelectric conversion layer formation with composition.
[film forming]
For the example composition A~I made in Examples 1 to 4,9~13 and the Comparative Examples 1 to 5 and compare
The film forming on alkali-free glass substrate of example composition a~e is evaluated by visual observation.
Zero: not seeing crackle, the removing of thermoelectric conversion layer.
×: it can see crackle, the removing of thermoelectric conversion layer.
[sheet resistance value]
For having obtained the sample of thermoelectric conversion layer, 3 points of sheet resistance value is measured using Loresta GP, by 3 points
Sheet resistance value of the average value as thermoelectric conversion layer.
[volume resistivity]
By sheet resistance value and film thickness measuring as a result, having calculated volume resistivity according to following formulas.
Volume resistivity (m Ω cm)=sheet resistance value (Ω/) × film thickness (μm) × 10-1
[embodiment 22]
It is dissolved in the HPMC-1 (1.5g, 1 mass parts) as polysaccharide in water (118.5g, 79 mass parts).It is added to
Ca3Co4O9(22.5g, 15 mass parts) and normal propyl alcohol (7.5g, 5 mass parts).The zirconium oxide bead for further adding φ 1mm, uses
Sand mill (500rpm) ball-milling treatment 4 hours, has obtained example composition J.
[embodiment 23]
The example composition J for dripping a small amount of on alkali-free glass substrate (25mm × 25mm), uses spin-coating method
(700rpm) forms film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour, obtains at 600 DEG C
Embodiment layer J1.Embodiment layer J1 also can't see crackle, removing after 100 DEG C of drying and after 600 DEG C of firings of film, really
Recognize and equably covers on the glass substrate.Film forming, sheet resistance value and the volume electricity of embodiment layer J1 is shown in table 7
Resistance rate.
[embodiment 24]
The example composition J for dripping a small amount of on alkali-free glass substrate (25mm × 25mm), uses spin-coating method
(700rpm) forms film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour, obtains at 350 DEG C
Embodiment layer J2.Film forming, sheet resistance value and the volume resistivity of embodiment layer J2 is shown in table 7.
Table 7
[embodiment 25]
The example composition J for dripping a small amount of on aluminum oxide substrate (15mm × 15mm) is used spin-coating method (700rpm)
Form film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour at 600 DEG C, has obtained embodiment layer
J3。
[embodiment 26]
The example composition J for dripping a small amount of on (15mm × 15mm) on aluminum oxide substrate, uses spin-coating method
(700rpm) forms film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt into 1 hour, obtains at 350 DEG C
Embodiment layer J4.
[embodiment 27]
About the Seebeck coefficient of the embodiment layer J3 formed on aluminum oxide substrate, 100 DEG C, 350 are heated to by making
DEG C or the face of 600 DEG C of embodiment layer J3 in generate 0~5 DEG C of temperature difference, and measure the voltage generated at this time and calculate.In table
The Seebeck coefficient of embodiment layer J3 is shown in 8.Since embodiment layer J3 has the Seebeck coefficient of 50 μ V/K or more, so energy
It enough confirms with heat to electricity conversion ability.About embodiment layer J4, is also calculated using same method and be heated to 100 DEG C, 350
DEG C embodiment layer Seebeck coefficient.The Seebeck coefficient of embodiment layer J4 is shown in table 8.Since embodiment layer J4 also has
There is the Seebeck coefficient of 50 μ V/K or more, so being able to confirm that with heat to electricity conversion ability.
Table 8
[embodiment 28]
Example composition A is formd into painting on alkali-free glass substrate (25mm × 25mm) using spin-coating method (700rpm)
Film.Obtained film is 5 minutes dry at 100 DEG C, it is then burnt at 350 DEG C 1 hour, film is finally subjected to light sintering
(voltage 3000V, 300 μ s), to obtain embodiment layer A4.The film thickness of embodiment layer A4 is 0.8 μm, and volume resistivity is
3.1×102mΩcm。
Claims (7)
1. a kind of thermoelectric conversion layer, which is formed, uses composition, it includes (A) water, (B) cobalt system's oxide and (C) polysaccharide,
Relative to 100 mass parts of the composition, (A) water adds up to 90~99.98 mass parts with (B) cobalt system oxide, (B) cobalt
It is oxide for 1~50 mass parts, (C) polysaccharide is 0.02~10 mass parts.
2. thermoelectric conversion layer according to claim 1, which is formed, uses composition,
(C) polysaccharide is cellulose derivative.
3. thermoelectric conversion layer according to claim 2, which is formed, uses composition,
The cellulose derivative is hydroxypropyl methyl cellulose.
4. described in any item thermoelectric conversion layers according to claim 1~3, which are formed, uses composition,
(B) cobalt system oxide is the compound indicated with following general formulas (1), general formula (2) or general formula (3),
Caa1A1 b1Coc1A2 d1Oe1 (1)
In formula (1), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and group of the lanthanides member
Element at least one of element, A2Be selected from Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least one of
Element, 2.2≤a1≤3.6,0≤b1≤0.8,2.0≤c1≤4.5,0≤d1≤2.0,8≤e1≤10；
Naa2A1 b2Coc2A2 d2Oe2 (2)
In formula (2), A1It is selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and group of the lanthanides member
Element at least one of element, A2Be selected from Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta at least one of
Element, the 0 < < of a2≤2,0≤b2≤0.6,0 c2≤2,0≤d2≤0.6,1.0≤e2≤3.0；
Bia3M1 f3A1 b3Coc3A2 d3Oe3 (3)
In formula (3), M1It is Sr or Pb, A1Be selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al,
Bi, Y and lanthanide series at least one of element, A2Be selected from Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta it
At least one of element, 1.8≤a3≤2.2,0≤f3≤0.4,1.8≤b3≤2.2,1.6≤c3≤2.2,0≤d3≤
0.5,8≤e3≤10.
5. a kind of manufacturing method of thermoelectric conversion layer, comprising:
The work of envelope is formed with composition to described in any item thermoelectric conversion layer formation of coating of substrates Claims 1 to 4
Sequence；With
Then, the work being burnt into the envelope in 300 DEG C or more of oxidizing atmosphere to remove polysaccharide from the envelope
Sequence.
6. a kind of manufacturing method of thermoelectric conversion layer, comprising:
The work of envelope is formed with composition to described in any item thermoelectric conversion layer formation of coating of substrates Claims 1-4
Sequence；With
Then, the envelope is subjected to light firing by light irradiation in oxidizing atmosphere in order to remove polysaccharide from the envelope
Process.
7. a kind of manufacturing method of thermoelectric conversion layer, comprising:
The work of envelope is formed with composition to described in any item thermoelectric conversion layer formation of coating of substrates Claims 1-4
Sequence；
The process for being burnt into the envelope in 300 DEG C or more of oxidizing atmosphere to remove polysaccharide from the envelope；With
And then the process that the envelope is subjected to light firing by light irradiation in oxidizing atmosphere.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016184454 | 2016-09-21 | ||
| JP2016-184454 | 2016-09-21 | ||
| PCT/JP2017/034140 WO2018056368A1 (en) | 2016-09-21 | 2017-09-21 | Composition for thermoelectric conversion layer formation and method for producing thermoelectric conversion layer |
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| CN109716546A true CN109716546A (en) | 2019-05-03 |
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| JP (1) | JPWO2018056368A1 (en) |
| CN (1) | CN109716546A (en) |
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| WO2019181960A1 (en) * | 2018-03-20 | 2019-09-26 | 日産化学株式会社 | Composition for forming thermoelectric conversion layer and method for producing thermoelectric conversion layer |
Citations (7)
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|---|---|---|---|---|
| JP2003229605A (en) * | 2001-11-29 | 2003-08-15 | Sk Kaken Co Ltd | Thermoelectric conversion material and its manufacturing method |
| JP2003277147A (en) * | 2002-03-25 | 2003-10-02 | National Institute Of Advanced Industrial & Technology | Method for producing metal oxide sintered compact |
| CN101156256A (en) * | 2005-04-13 | 2008-04-02 | 住友化学株式会社 | Thermoelectric conversion material, method for production thereof and thermoelectric conversion element |
| CN101542762A (en) * | 2006-11-28 | 2009-09-23 | 住友化学株式会社 | Thermoelectric conversion material and thermoelectric conversion element |
| CN102443290A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
| CN104205383A (en) * | 2012-03-21 | 2014-12-10 | 琳得科株式会社 | Thermoelectric conversion material and method for manufacturing same |
| CN105359286A (en) * | 2013-07-03 | 2016-02-24 | 富士胶片株式会社 | Thermoelectric-conversion-layer manufacturing method and thermoelectric conversion element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3565503B2 (en) * | 2000-09-07 | 2004-09-15 | 大研化学工業株式会社 | Oxide thermoelectric conversion material |
| US8044292B2 (en) * | 2006-10-13 | 2011-10-25 | Toyota Motor Engineering & Manufacturing North America, Inc. | Homogeneous thermoelectric nanocomposite using core-shell nanoparticles |
-
2017
- 2017-09-21 JP JP2018540298A patent/JPWO2018056368A1/en not_active Withdrawn
- 2017-09-21 WO PCT/JP2017/034140 patent/WO2018056368A1/en active Application Filing
- 2017-09-21 CN CN201780057189.XA patent/CN109716546A/en active Pending
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003229605A (en) * | 2001-11-29 | 2003-08-15 | Sk Kaken Co Ltd | Thermoelectric conversion material and its manufacturing method |
| JP2003277147A (en) * | 2002-03-25 | 2003-10-02 | National Institute Of Advanced Industrial & Technology | Method for producing metal oxide sintered compact |
| CN101156256A (en) * | 2005-04-13 | 2008-04-02 | 住友化学株式会社 | Thermoelectric conversion material, method for production thereof and thermoelectric conversion element |
| CN101542762A (en) * | 2006-11-28 | 2009-09-23 | 住友化学株式会社 | Thermoelectric conversion material and thermoelectric conversion element |
| CN102443290A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
| CN104205383A (en) * | 2012-03-21 | 2014-12-10 | 琳得科株式会社 | Thermoelectric conversion material and method for manufacturing same |
| CN105359286A (en) * | 2013-07-03 | 2016-02-24 | 富士胶片株式会社 | Thermoelectric-conversion-layer manufacturing method and thermoelectric conversion element |
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| JPWO2018056368A1 (en) | 2019-07-11 |
| WO2018056368A1 (en) | 2018-03-29 |
| TW201829572A (en) | 2018-08-16 |
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