CN109994595B - Thermoelectric conversion system based on solid-state nano-pores - Google Patents
Thermoelectric conversion system based on solid-state nano-pores Download PDFInfo
- Publication number
- CN109994595B CN109994595B CN201711474650.XA CN201711474650A CN109994595B CN 109994595 B CN109994595 B CN 109994595B CN 201711474650 A CN201711474650 A CN 201711474650A CN 109994595 B CN109994595 B CN 109994595B
- Authority
- CN
- China
- Prior art keywords
- thermoelectric conversion
- opening end
- electrolyte solution
- conversion system
- tapered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 22
- 239000011148 porous material Substances 0.000 title claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 18
- 239000002918 waste heat Substances 0.000 claims abstract description 12
- 229920006254 polymer film Polymers 0.000 claims abstract description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 3
- 229920005597 polymer membrane Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a thermoelectric conversion system based on solid-state nano holes, which is a closed system and comprises a container, a thermoelectric conversion device and a thermoelectric conversion device, wherein the container is divided into two parts by a polymer film with a tapered hole array; wherein one part is used for containing high-temperature electrolysis containing waste heat energyThe other part of the electrolyte solution is used for containing low-temperature electrolyte solution; electrodes are arranged in the two parts of containers and are connected by adopting a lead; the aperture of the big opening end of the tapered hole is 300-1000 nanometers, the aperture of the small opening end is 6-210 nanometers, and the hole density is 0.5x106‑1.5x106cm‑2(ii) a The large opening end of the conical hole of the polymer film with the conical hole array corresponds to the high-temperature electrolyte solution, and the small opening end corresponds to the low-temperature electrolyte solution. The invention has simple structure and easily obtained materials; the device is light and flexible, and can be suitable for various practical situations; the method is clean, green and environment-friendly, and has no pollution problem from device construction to practical application.
Description
Technical Field
The invention belongs to the technical field of energy utilization, and particularly relates to a thermoelectric conversion system based on solid-state nanopores.
Background
Energy is an important foundation for the development of human society, and the world energy demand is continuously increased along with the development of world economy, the rapid increase of world population and the continuous improvement of the living standard of people. The utilization of renewable energy sources in nature is crucial, wherein the renewable waste heat (aqueous solution with temperature less than 100 ℃) widely existing in nature is a promising energy source. Through the capture and storage of waste heat, the utilization efficiency of energy sources is improved, and the energy source problem can be relieved to a certain extent. Most of the existing waste heat capture systems are based on semiconductor thermoelectric materials. Although thermoelectric materials have various styles and high conversion efficiency, the pollution problem and high cost are factors for restricting further development. Particularly its relatively low efficiency in the field of waste heat capture, has made the use of semiconductor thermoelectric materials in this field even more influential. Therefore, it has been a desirable topic to develop a simple, green and low cost waste heat capture system.
Disclosure of Invention
The invention aims to provide a thermoelectric conversion system based on solid-state nano holes, which is a brand-new liquid-state thermoelectric conversion system and can convert external heat energy into electric energy by utilizing the ion directional flow of the bionic nano holes. Through verification of theories and experiments, the invention can convert different heat energy into corresponding electric energy.
In order to achieve the purpose, the invention adopts the following technical scheme:
a solid-state nanopore-based thermoelectric conversion system, the thermoelectric conversion system being a closed system comprising a container separated into two parts by a polymeric membrane having an array of tapered pores;
wherein one part is used for containing high-temperature electrolyte solution containing waste heat energy, and the other part is used for containing low-temperature electrolyte solution; electrodes are arranged in the two parts of containers and are connected by adopting a lead;
the aperture of the big opening end of the tapered hole is 300-1000 nanometers, the aperture of the small opening end is 6-210 nanometers, and the hole density is 0.5x106-1.5x106cm-2；
The large opening end of the conical hole of the polymer film with the conical hole array corresponds to the high-temperature electrolyte solution, and the small opening end corresponds to the low-temperature electrolyte solution.
Preferably, the electrode is an Ag/AgCl electrode or an indium tin oxide sputtered PET flexible electrode.
Preferably, the aperture of the big opening end of the conical hole is 500 nanometers, the aperture of the small opening end is 10-30 nanometers, and the hole density is 1x106cm-2。
Preferably, the electrolyte used in this system has a KCl concentration of 1M.
The polymer film with the conical hole array is a porous polyimide film with the conical hole array.
The tapered hole of the nano polymer is a tapered structure with different apertures at two ends: the aperture of one end is about 500 nanometers, which is called as a big-mouth end; and the aperture of the other end is about 10 nanometers and is also called as a small opening end.
The membrane used in the present invention was a porous PI membrane of the same pore array (pore density: 1X 10)6cm-2). The surface charge density of the porous PI film is-0.23C/m2。
The invention utilizes asymmetric conical Polymer (PI) nano-pores, KCl solution as electrolyte and PET sputtered by Indium Tin Oxide (ITO) as flexible electrode to construct a simple and stable waste heat capture system.
Specifically, the thermoelectric conversion system in the present invention is a closed system, and the left container contains a high-temperature electrolyte solution containing waste heat energy, corresponding to the right container containing a low-temperature (room temperature) electrolyte solution. An anode or a cathode is arranged in the left container, and the anode or the cathode is arranged in the right container correspondingly; and the lead of the anode or the cathode arranged in the left container is led out of the left container, the lead corresponding to the cathode or the anode arranged in the right container is led out of the right container, and the circuit is communicated through an external ammeter and a load resistor.
The thermoelectric conversion system (waste heat capture system) of the present invention has the following advantages: the structure is simple, and the materials are easy to obtain; the device is light and flexible, and can be suitable for various practical situations; the method is clean, green and environment-friendly, and has no pollution problem from device construction to practical application; has good stability, and still has no obvious signal attenuation after multiple cycles.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a polymer film having an array of tapered holes according to the present invention;
FIG. 2 is a schematic diagram of the structure of a thermoelectric conversion system of the present invention;
FIG. 3 is an electron micrograph of tapered holes in a polymer film having an array of tapered holes according to the present invention.
Detailed Description
The following examples are intended to further illustrate the technical aspects of the present invention, but are not intended to limit the technical aspects of the present invention.
Example 1
(1) Tapered polymer nanopore preparation and characterization
As shown in FIG. 1, the tapered polymer nanopores of the porous polyimide film with the tapered pore array are prepared from Polyimide (PI) bombarded by heavy ions by a track etching method, wherein the etching solution is 13% NaClO, the blocking solution is 1M KI, and the etching temperature is 60 ℃. After etching for 1 hour, the substrate is washed with deionized water for standby. The prepared tapered porous membrane is characterized by an electron microscope, as shown in fig. 3, and the aperture of the large opening end and the small opening end of the tapered pore are both in the nanometer level as can be seen from fig. 3.
(2) Thermoelectric conversion system
As shown in fig. 2, a solid-state nanopore-based thermoelectric conversion system is a closed system comprising a container divided into two parts by a polymer thin film having an array of tapered pores;
wherein one part is used for containing high-temperature electrolyte solution containing waste heat energy, and the other part is used for containing low-temperature electrolyte solution; electrodes are arranged in the two parts of containers and are connected by adopting a lead;
the aperture of the big opening end of the tapered hole is 500 nanometers, the aperture of the small opening end of the tapered hole is 10 nanometers, and the hole density is 1x106cm-2；
The large opening end of the conical hole of the polymer film with the conical hole array corresponds to the high-temperature electrolyte solution, and the small opening end corresponds to the low-temperature electrolyte solution.
The electrode is an Ag/AgCl electrode or a PET flexible electrode sputtered by indium tin oxide.
(3) Osmotic energy conversion Performance test
The left side of the test cell is placed with 35 ℃ KCl (1M) solution, the right side is placed with 25 ℃ KCl (1M) solution, one side of the small end corresponds to low temperature KCl (1M) solution, and the maximum output power is about 0.012mW/M2。
Placing KCl (1M) solution at 45 ℃ on the left side of the test cell, placing KCl (1M) solution at 25 ℃ on the right side, corresponding to KCl (1M) solution at low temperature on the side of small end, and having maximum output power of about 0.064mW/M2。
Placing KCl (1M) solution at 55 ℃ on the left side of the test cell, and placing KCl (1M) solution at 25 ℃ on the right side of the test cellThe side of the small end of the liquid corresponds to a low-temperature KCl (1M) solution, and the maximum output power is about 0.09mW/M2。
Placing KCl (1M) solution at 65 ℃ on the left side of the test cell, placing KCl (1M) solution at 25 ℃ on the right side, corresponding to KCl (1M) solution at low temperature on the side of small end, and having maximum output power of about 0.18mW/M2。
Placing KCl (1M) solution at 65 ℃ on the left side of the test cell, placing KCl (1M) solution at 25 ℃ on the right side, corresponding to KCl (1M) solution at low temperature on the side of small end, and having maximum output power of about 0.18mW/M2。
Placing KCl (1M) solution at 75 deg.C on the left side of the test cell, placing KCl (1M) solution at 25 deg.C on the right side, corresponding to KCl (1M) solution at low temperature on the side of small end, and outputting maximum power of 0.21mW/M2。
From the above tests, it can be seen that the hot spot switching power of the present invention has a positive correlation with the transmembrane temperature difference, and the larger the temperature difference is, the larger the output power is.
The small end of the conical hole used in the invention determines the ion selectivity, and the smaller the hole diameter, the better the selectivity. But the corresponding membrane resistance will also increase and the ion current will decrease.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A solid state nanopore based thermoelectric conversion system, wherein the thermoelectric conversion system is a closed system comprising a container divided into two parts by a polymeric membrane having an array of tapered pores;
wherein one part is used for containing high-temperature electrolyte solution containing waste heat energy, and the other part is used for containing low-temperature electrolyte solution; electrodes are arranged in the two parts of containers and are connected by adopting a lead;
the aperture of the big opening end of the tapered hole is 300-1000 nanometers, the aperture of the small opening end is 6-210 nanometers, and the hole density is 0.5x106-1.5x106cm-2；
The large opening end of the conical hole of the polymer film with the conical hole array corresponds to the high-temperature electrolyte solution, and the small opening end corresponds to the low-temperature electrolyte solution.
2. The solid state nanopore based thermoelectric conversion system of claim 1, wherein the electrode is an Ag/AgCl electrode or an indium tin oxide sputtered PET flexible electrode.
3. The solid-state nanopore based thermoelectric conversion system of claim 1, wherein the tapered pore has a pore diameter of 500 nm at the large-mouth end, a pore diameter of 10-30 nm at the small-mouth end, and a pore density of 1x106cm-2。
4. The solid state nanopore based thermoelectric conversion system of claim 1, wherein the polymer membrane having an array of tapered pores is a porous polyimide membrane having an array of tapered pores.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711474650.XA CN109994595B (en) | 2017-12-29 | 2017-12-29 | Thermoelectric conversion system based on solid-state nano-pores |
| PCT/CN2018/085930 WO2019128029A1 (en) | 2017-12-29 | 2018-05-08 | Thermoelectric conversion system based on solid state nanopores |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711474650.XA CN109994595B (en) | 2017-12-29 | 2017-12-29 | Thermoelectric conversion system based on solid-state nano-pores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109994595A CN109994595A (en) | 2019-07-09 |
| CN109994595B true CN109994595B (en) | 2020-08-04 |
Family
ID=67062960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711474650.XA Expired - Fee Related CN109994595B (en) | 2017-12-29 | 2017-12-29 | Thermoelectric conversion system based on solid-state nano-pores |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109994595B (en) |
| WO (1) | WO2019128029A1 (en) |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076809A (en) * | 1992-10-29 | 1993-09-29 | 科尔涅伊·D·托夫斯蒂尤克 | Capacitive thermoelectric device |
| EP2338536B1 (en) * | 2009-12-21 | 2015-08-05 | Biotronik VI Patent AG | Biocorrodible implants having a functionalized coating |
| CN102381683B (en) * | 2010-09-03 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Electrochemical method and materials for preparation of layered sheet alloy thermoelectric materials |
| EP2769420A4 (en) * | 2011-10-21 | 2015-07-22 | Nanoconversion Technologies Inc | Thermoelectric converter with projecting cell stack |
| US9267714B2 (en) * | 2012-11-08 | 2016-02-23 | B/E Aerospace, Inc. | Thermoelectric cooling device including a liquid heat exchanger disposed between air heat exchangers |
| CN102983262A (en) * | 2012-12-16 | 2013-03-20 | 邱德祥 | Electrolyte thermoelectric cell |
| EP2973762A4 (en) * | 2013-03-15 | 2016-08-24 | Thomas Beretich | Adverse event-resilient network system |
| CN104811092B (en) * | 2015-05-19 | 2017-05-31 | 武汉大学 | A kind of system generated electricity using liquid pyroelectric effect |
| CN105107393B (en) * | 2015-09-28 | 2017-07-28 | 河北工业大学 | A kind of preparation method of the selective composite membrane of the monovalention based on template |
| CN205542900U (en) * | 2016-03-11 | 2016-08-31 | 武汉黄特科技发展有限公司 | Electrolyte thermoelectric cell with guide electrode |
| CN106449961B (en) * | 2016-11-01 | 2019-02-15 | 中国工程物理研究院化工材料研究所 | The electrode structure and electrolyte thermoelectric cell preparation method of electrolyte thermoelectric cell |
| CN106992716B (en) * | 2017-05-12 | 2024-01-19 | 长沙理工大学 | Reverse electrodialysis heat energy power generation device and method |
-
2017
- 2017-12-29 CN CN201711474650.XA patent/CN109994595B/en not_active Expired - Fee Related
-
2018
- 2018-05-08 WO PCT/CN2018/085930 patent/WO2019128029A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019128029A1 (en) | 2019-07-04 |
| CN109994595A (en) | 2019-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Smart bioinspired nanochannels and their applications in energy‐conversion systems | |
| Kwon et al. | Energy harvesting system using reverse electrodialysis with nanoporous polycarbonate track‐etch membranes | |
| Zhang et al. | Sustainable power generation for at least one month from ambient humidity using unique nanofluidic diode | |
| KR101511990B1 (en) | Ion exchange membrane used for reverse electrodialysis device and reverse electrodialysis device including the same | |
| US9982104B2 (en) | Reverse electrodialysis device having enhanced maximum power density with ultra-thin ion exchange membranes | |
| KR101513446B1 (en) | Ion exchange membrane used for flow-electrode capacitive deionization device and flow-electrode capacitive deionization device including the same | |
| WO2020147443A1 (en) | Moisture power generation method and equipment | |
| CN110170253A (en) | Two dimension/one-dimensional heterogeneous nanochannel film, preparation method and application | |
| Chen et al. | Hierarchical porous poly (ether sulfone) membranes with excellent capacity retention for vanadium flow battery application | |
| CN108927019B (en) | Preparation method of block copolymer membrane and functional porous membrane hybridized salt difference power generation membrane | |
| Hu et al. | Bioinspired poly (ionic liquid) membrane for efficient salinity gradient energy harvesting: Electrostatic crosslinking induced hierarchical nanoporous network | |
| CN103762375A (en) | Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery | |
| Zhao et al. | Water‐Enabled Electricity Generation: A Perspective | |
| CN103996856B (en) | Codope polypyrrole material and its preparation method and application | |
| Jiang et al. | Simultaneous electricity generation and steam production from a wide range of salinity by using unique nanofluidic diode | |
| Wang et al. | Graphene modified polyacrylonitrile fiber as high-performance cathode for marine sediment microbial fuel cells | |
| CN105734831B (en) | A kind of carbon nano-fiber felt and its preparation and the application in all-vanadium flow battery | |
| Vlasov et al. | Ion-exchange membrane impact on preferential water transfer in all-vanadium redox flow battery | |
| CN109994595B (en) | Thermoelectric conversion system based on solid-state nano-pores | |
| CN107546038B (en) | A kind of concentration difference capacitor | |
| Zhang et al. | Nanofiltration membranes for vanadium flow battery application | |
| CN109453808A (en) | A kind of graphene/Pt/Polypyrrole composite material preparation method and applications of three-dimensional multistage hole | |
| CN104962078A (en) | Biodegradable composite stable polymer electrolyte membrane | |
| CN109755620B (en) | Zinc-iodine flow battery | |
| Chandrasekaran et al. | Electrochemical study on aqueous magnesium nitrate electrolyte system for EDLC applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200804 |