CN106531875A - Light absorbing material layer for thermal energy collection of micro thermoelectric battery and manufacture method of light absorbing material layer - Google Patents
Light absorbing material layer for thermal energy collection of micro thermoelectric battery and manufacture method of light absorbing material layer Download PDFInfo
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- CN106531875A CN106531875A CN201610910725.3A CN201610910725A CN106531875A CN 106531875 A CN106531875 A CN 106531875A CN 201610910725 A CN201610910725 A CN 201610910725A CN 106531875 A CN106531875 A CN 106531875A
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- 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
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Abstract
The present invention relates to a light absorbing material layer for the thermal energy collection of a micro thermoelectric battery and a manufacture method of the light absorbing material layer. The light absorbing material layer is a nickel-based ternary alloy having a light absorption characteristic which is prepared on the surface of a conductive base material; the thickness of the nickel-based ternary alloy ranges from 1 micron to 500 microns; the nickel-based ternary alloy is black; the structure of the nickel-based ternary alloy is loose; the thickness of the conductive base material ranges from 0.1 mm to 2 mm; an aqueous solution is adopted as an electroplating solution; nickel ion-containing salt, sulfur ion-containing salt, conductive salt, a complexing agent and a pH buffer agent are added into the electroplating solution; the light absorbing material layer is arranged at the hot end of the micro thermoelectric battery; and under the irradiation of sunlight, the light absorbing material layer can directly convert sunlight irradiated on thereon to heat and transfer the heat to the hot end of the micro thermoelectric battery, and therefore, the temperature of the hot end of the micro thermoelectric battery can be improved, and therefore, large temperature difference can be realized between the hot end and cold end of the micro thermoelectric battery conveniently, and the output power of the micro thermoelectric battery can be improved.
Description
Technical field
The present invention relates to thermoelectric cell technical field, more particularly to a kind of extinction for minitype thermoelectric cell thermal energy collecting
Material layer and its manufacture method.
Background technology
Thermoelectric cell is a kind of physical power source, by the electrically coupled in series of wherein p-type and N-shaped thermoelectric material, in thermoelectric cell
Under conditions of hot junction and cold end have the temperature difference, electric energy is externally exported.The temperature difference between the hot junction of thermoelectric cell and cold end is bigger, electricity
The power that pond externally exports is also bigger.It is to set up the temperature difference as big as possible between the hot junction of thermoelectric cell and cold end, generally
In the cold end of thermoelectric cell, fin is set.If the temperature in thermoelectric cell hot junction can be improved, in the hot junction of thermoelectric cell and cold
The bigger temperature difference will be set up between end, advantageously in the power output for improving thermoelectric cell.
The present invention proposes a kind of light-absorbing material layer for minitype thermoelectric cell thermal energy collecting and its manufacture method.Using
Electric plating method manufactures light-absorbing material layer.Light-absorbing material layer is positioned over the hot junction of minitype thermoelectric cell.Light-absorbing material layer will can be inhaled
The sunshine of receipts is directly translated into heat transfer and gives minitype thermoelectric cell hot junction, is conducive in the hot junction of minitype thermoelectric cell and cold
The bigger temperature difference is set up between end, improves the power output of minitype thermoelectric cell.
The content of the invention
The present invention proposes a kind of light-absorbing material layer for minitype thermoelectric cell thermal energy collecting and its manufacture method.Extinction
Material layer is prepared on the Ni-based ternary alloy three-partalloy with extinction characteristic on conductive substrate material surface, including Ni S Mo alloys,
Ni S Co alloys, Ni S Fe alloys, Ni S P alloys and Ni S Zn alloys.Using electric plating method in conductive substrate material
Surface manufactures light-absorbing material layer., in 1 micron 500 microns of scope, in black, structure is more loose for the thickness of Ni-based ternary alloy three-partalloy.
The thickness of conductive substrate material is in 0.1 millimeter 2 millimeters of scope.
Electroplating solution is the aqueous solution, is wherein added with the salt containing nickel ion, the salt of sulfur-containing anion, conducting salt, complexing agent, pH
Buffer.Additionally, the salt containing molybdenum ion in the solution of electroplated Ni S Mo alloys, is also added with, the solution of electroplated Ni S Co alloys
In be also added with the salt containing cobalt ions, be also added with the salt containing iron ion, electroplated Ni S P in the solution of electroplated Ni S Fe alloys
The salt containing phosphonium ion is also added with the solution of alloy, is also added with the salt containing zinc ion in the solution of electroplated Ni S Zn alloys.
The method of plating light-absorbing material layer is comprised the following steps：
1) prepare electroplating solution.Electroplating solution is the aqueous solution.Salt containing relevant ions is added in distilled water, stirring makes which
Dissolving.Add conducting salt, complexing agent, pH buffer.The solution for preparing is put in coating bath.
2) bath temperature in coating bath is adjusted to the temperature range of suitable electroplate light absorbent 20 60 DEG C.
3) by the pH value of plating solution in coating bath adjust to it is suitable plating light absorbent 36 scope.
4) galvanic anode is put into into plating solution, and is connected to the positive pole of electroplating power supply.
5) will be connected with the negative pole of electroplating power supply for manufacturing the conductive substrate material of light-absorbing material layer, control the electricity of plating
Current density is in 3 30mA/cm2Scope, it is powered enter groove electroplated.
6) after the thickness of the plating nickel-base ternary alloy three-partalloy on conductive substrate material surface reaches predetermined thickness, it is drawn off plating
Groove, cleans, dries up.
Can be nickel sulfate, nickel chloride, amino for electroplating the salt containing nickel ion added in the plating solution of light-absorbing material layer
It is more than the one or two kinds of in nickel sulphonic acid and ammonium nickel sulfate.Model of the concentration of the salt containing nickel ion in 10 60g/L in plating solution
Enclose.
Salt for electroplating the sulfur-containing anion added in the plating solution of light-absorbing material layer can be sodium sulfocyanate, potassium rhodanide and
It is more than the one or two kinds of in ammonium thiocyanate.Scope of the concentration of the salt of sulfur-containing anion in 10 50g/L in plating solution.
For electroplate the complexing agent added in the plating solution of light-absorbing material layer can be tartaric acid, sodium potassium tartrate tetrahydrate, citric acid,
Ammonium citrate, EDTA.Scope of the concentration of plating solution complexing agent in 10 100g/L.
Can be sodium chloride, potassium chloride, sodium sulphate, sulfuric acid for electroplating the conducting salt added in the plating solution of light-absorbing material layer
Potassium.Scope of the concentration of conducting salt in 10 30g/L in plating solution.
Can be boric acid, or HAc and NaAc for electroplating the pH buffer added in the plating solution of light-absorbing material layer.
Scope of the concentration of pH buffer in 10 40g/L in plating solution.
The salt containing molybdenum ion added in the solution of electroplated Ni S Mo alloys can be ammonium molybdate, sodium molybdate, potassium molybdate.
Scope of the concentration of the salt containing molybdenum ion in 10 60g/L in plating solution.
The salt containing zinc ion added in the solution of electroplated Ni S Zn alloys can be zinc chloride, zinc sulfate.Contain in plating solution
Scope of the concentration of the salt of zinc ion in 10 60g/L.
The salt containing cobalt ions added in the solution of electroplated Ni S Co alloys can be cobaltous sulfate, cobalt chloride, sulfamic acid
Cobalt.Scope of the concentration of the salt containing cobalt ions in 10 60g/L in plating solution.
The salt containing iron ion added in the solution of electroplated Ni S Fe alloys can be ferric sulfate.Contain iron ion in plating solution
Salt concentration 10 60g/L scope.
The salt containing phosphonium ion added in the solution of electroplated Ni S P alloys can be sodium hypophosphite, potassium hypophosphite, phosphoric acid
Sodium, potassium phosphate.Scope of the concentration of the salt containing phosphonium ion in 10 50g/L in plating solution.
Conductive substrate material for plating nickel-base ternary alloy three-partalloy can be that metallic copper and copper alloy, metallic nickel and nickel are closed
Gold, stainless steel.
The present invention proposes a kind of light-absorbing material layer for minitype thermoelectric cell thermal energy collecting and its manufacture method.Extinction
Material layer is positioned over the hot junction of minitype thermoelectric cell.Light-absorbing material layer under sunlight, can be emitted onto thereon
Sunshine is directly translated into heat transfer and gives minitype thermoelectric cell hot junction, improves the temperature in minitype thermoelectric cell hot junction, is conducive to
The bigger temperature difference is set up between the hot junction of minitype thermoelectric cell and cold end, improves the power output of minitype thermoelectric cell.
Specific embodiment
Embodiment one：Copper sheet with 0.1mm thickness, is manufactured as conductive substrate material in its electroplating surface Ni S Mo alloys
For the light absorbent layer material of minitype thermoelectric cell thermal energy collecting
By nickel sulfate (30g/L), sodium sulfocyanate (30g/L), ammonium molybdate (20g/L), sodium potassium tartrate tetrahydrate (80g/L), boric acid
(30g/L), sodium sulphate (20g/L) add distilled water in and dissolve which, control bath pH value be 3, temperature 60 C, the electricity of plating
Current density is in 3mA/cm2, take out after electroplating 1 hour, the Ni S Mo light-absorbing material layer materials of black are produced on conductive copper sheet surface
Material.The hot junction of minitype thermoelectric cell is placed on, the power output that can improve minitype thermoelectric cell under sunlight exceedes
50%.
Ammonium molybdate therein can also be replaced with sodium molybdate or potassium molybdate.
Embodiment two：Nickel sheet with 3mm thickness as conductive substrate material, in its electroplating surface Ni S P alloys, use by manufacture
In the light absorbent layer material of minitype thermoelectric cell thermal energy collecting
By nickel chloride (60g/L), potassium rhodanide (50g/L), sodium hypophosphite (30g/L), citric acid (100g/L), HAc
(40g/L), NaAc (40g/L), sodium chloride (10g/L) add distilled water in and dissolve which.It is 5 to control bath pH value, temperature
20 DEG C, the current density of plating is in 30mA/cm2, take out after electroplating 3 hours, the Ni S of black are produced on conductive copper sheet surface
P light absorbent layer materials.The hot junction of minitype thermoelectric cell is placed on, the defeated of minitype thermoelectric cell under sunlight, can be improved
Go out power more than 60%.
Sodium hypophosphite therein can also be replaced with potassium hypophosphite.
Embodiment three：Silver strip with 1mm thickness as conductive substrate material, in its electroplating surface Ni S Co alloys, use by manufacture
In the light absorbent layer material of minitype thermoelectric cell thermal energy collecting.
By nickel sulfamic acid (40g/L), ammonium thiocyanate (10g/L), sulfamic acid cobalt (50g/L), potassium chloride (30g/L),
Boric acid (40g/L) add distilled water in and dissolve which.It is 4 to control bath pH value, 40 DEG C of temperature, and the current density of plating exists
20mA/cm2, take out after electroplating 2 hours, the Ni S Co light absorbent layer materials of black are produced on conductive copper sheet surface.By its
The hot junction of minitype thermoelectric cell is placed in, the power output of minitype thermoelectric cell can be improved under sunlight more than 60%.
Nickel sulfamic acid therein can also be replaced with nickel sulfate.Sulfamic acid cobalt therein can also be replaced with cobaltous sulfate
Change.
Example IV：Alcu alloy film with 2mm thickness, is made as conductive substrate material in its electroplating surface Ni S Zn alloys
Make the light absorbent layer material for minitype thermoelectric cell thermal energy collecting
By ammonium nickel sulfate (10g/L), ammonium thiocyanate (10g/L), zinc sulfate (60g/L), EDTA (80g/L), sodium sulphate
(30g/L), boric acid (10g/L) add distilled water in and dissolve which.It is 4 to control bath pH value, temperature 50 C, the electric current of plating
Density is in 10mA/cm2, take out after electroplating 3 hours, the Ni S Zn light-absorbing material layer materials of black are produced on conductive copper sheet surface
Material.The hot junction of minitype thermoelectric cell is placed on, the power output that can improve minitype thermoelectric cell under sunlight exceedes
40%.
Zinc sulfate therein can also be replaced with zinc chloride.
Embodiment five：Stainless steel substrates with 1.5mm thickness as conductive substrate material, in its electroplating surface Ni S Fe alloys,
Manufacture the light absorbent layer material for minitype thermoelectric cell thermal energy collecting
By nickel sulfate (25g/L), potassium rhodanide (25g/L), ferric sulfate (30g/L), tartaric acid (60g/L), sodium sulphate
(60g/L), boric acid (25g/L) add distilled water in and dissolve which.It is 3 to control bath pH value, 40 DEG C of temperature, the electric current of plating
Density is in 15mA/cm2, take out after electroplating 2 hours, the Ni S Fe light-absorbing material layer materials of black are produced on conductive copper sheet surface
Material.The hot junction of minitype thermoelectric cell is placed on, the power output that can improve minitype thermoelectric cell under sunlight exceedes
60%.
Claims (9)
1. a kind of light-absorbing material layer for minitype thermoelectric cell thermal energy collecting；It is characterized in that arranging on conductive substrate material surface
There is the Ni-based ternary alloy layer of extinction characteristic, the thickness of Ni-based ternary alloy three-partalloy is at 1 micron -500 microns.
2. material layer as claimed in claim 1, is characterized in that described Ni-based ternary alloy three-partalloy includes Ni-S-Mo alloys, Ni-S-
Co alloys, Ni-S-Fe alloys, Ni-S-P alloys or Ni-S-Zn alloys.
3. the preparation method of the light-absorbing material layer for minitype thermoelectric cell thermal energy collecting of claim 1, is characterized in that step
It is as follows：
1) prepare electroplating solution：Electroplating solution is the aqueous solution, the salt containing relevant ions is added in distilled water, stirring and dissolving；Plus
Enter conducting salt, complexing agent, pH buffer, the solution for preparing is put in coating bath；
2) bath temperature in coating bath is adjusted to 20-60 DEG C；
3) pH value of plating solution in coating bath is adjusted to 3-6；
4) galvanic anode is put into into plating solution, and is connected to the positive pole of electroplating power supply；
5) will be connected with the negative pole of electroplating power supply for manufacturing the conductive substrate material of light-absorbing material layer, the electric current for controlling plating is close
Degree is in 3-30mA/cm2, it is powered enter groove electroplated；.
6) after the thickness of the plating nickel-base ternary alloy three-partalloy on conductive substrate material surface reaches predetermined thickness, coating bath is drawn off,
Clean, dry up.
4. method as claimed in claim 3, is characterized in that complexing agent is tartaric acid, sodium potassium tartrate tetrahydrate, citric acid, ammonium citrate
Or EDTA；Scope of the concentration of plating solution complexing agent in 10-100g/L.
5. method as claimed in claim 3, is characterized in that conducting salt is sodium chloride, potassium chloride, sodium sulphate or potassium sulfate；Plating solution
Scope of the concentration of middle conducting salt in 10-30g/L.
6. method as claimed in claim 3, is characterized in that pH buffer is boric acid, or HAc and NaAc；PH bufferings in plating solution
Scope of the concentration of agent in 10-40g/L.
7. method as claimed in claim 3, is characterized in that the salt of relevant ions includes the salt containing nickel ion, sulfur-containing anion
Salt, the salt containing molybdenum ion, the salt containing cobalt ions, the salt containing iron ion, the salt containing phosphonium ion or the salt containing zinc ion.
8. method as claimed in claim 7, it is characterized in that the salt containing nickel ion be nickel sulfate, nickel chloride, nickel sulfamic acid and
It is more than the one or two kinds of in ammonium nickel sulfate, the scope of the concentration of the salt of nickel ion in 10-60g/L；The salt of sulfur-containing anion is
More than the one or two kinds of in sodium sulfocyanate, potassium rhodanide and ammonium thiocyanate, the concentration of the salt of sulfur-containing anion is in 10-50g/L
Scope；Salt containing molybdenum ion is ammonium molybdate, sodium molybdate or potassium molybdate, the model of the concentration of the salt containing molybdenum ion in 10-60g/L
Enclose；Salt containing zinc ion is zinc chloride or zinc sulfate, the scope of the concentration of the salt containing zinc ion in 10-60g/L；Containing cobalt ions
Salt can be cobaltous sulfate, cobalt chloride or sulfamic acid cobalt, the scope of the concentration of the salt containing cobalt ions in 10-60g/L；Containing iron ion
Salt be ferric sulfate, the scope of the concentration of the salt containing iron ion in 10-60g/L；Salt containing phosphonium ion is sodium hypophosphite, hypophosphorous acid
Potassium, sodium phosphate or potassium phosphate, the scope of the concentration of the salt containing phosphonium ion in 10-50g/L.
9. method as claimed in claim 3, is characterized in that the conductive substrate material for plating nickel-base ternary alloy three-partalloy is metal
Copper and copper alloy, metallic nickel and nickel alloy, argent or stainless steel.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610910725.3A CN106531875A (en) | 2016-10-19 | 2016-10-19 | Light absorbing material layer for thermal energy collection of micro thermoelectric battery and manufacture method of light absorbing material layer |
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| CN201610910725.3A CN106531875A (en) | 2016-10-19 | 2016-10-19 | Light absorbing material layer for thermal energy collection of micro thermoelectric battery and manufacture method of light absorbing material layer |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2847686Y (en) * | 2005-12-19 | 2006-12-13 | 中国科学院广州能源研究所 | Light focusing heat collecting type solar energy temperature differential generator |
| CN101814867A (en) * | 2009-02-20 | 2010-08-25 | 清华大学 | Thermoelectric generator |
| US20120180840A1 (en) * | 2006-11-13 | 2012-07-19 | Massachusetts Institute Of Technology | Solar thermoelectric conversion |
| WO2013173450A9 (en) * | 2012-05-15 | 2014-03-13 | Sheetak, Inc. | Integrated selective wavelength absorber solar thermoelectric generator |
-
2016
- 2016-10-19 CN CN201610910725.3A patent/CN106531875A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2847686Y (en) * | 2005-12-19 | 2006-12-13 | 中国科学院广州能源研究所 | Light focusing heat collecting type solar energy temperature differential generator |
| US20120180840A1 (en) * | 2006-11-13 | 2012-07-19 | Massachusetts Institute Of Technology | Solar thermoelectric conversion |
| CN101814867A (en) * | 2009-02-20 | 2010-08-25 | 清华大学 | Thermoelectric generator |
| WO2013173450A9 (en) * | 2012-05-15 | 2014-03-13 | Sheetak, Inc. | Integrated selective wavelength absorber solar thermoelectric generator |
Non-Patent Citations (2)
| Title |
|---|
| FENG CAO, ET AL.: "《A review of cermet-based spectrally selective solar absorbers》", 《ENERGY ENVIRON. SCI.》 * |
| 詹兴刚: "《电镀黑镍工艺的应用》", 《涂装与电镀》 * |
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Application publication date: 20170322 |