CN113506686B - Thermal charging type capacitor and preparation method thereof - Google Patents

Thermal charging type capacitor and preparation method thereof Download PDF

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CN113506686B
CN113506686B CN202110634522.7A CN202110634522A CN113506686B CN 113506686 B CN113506686 B CN 113506686B CN 202110634522 A CN202110634522 A CN 202110634522A CN 113506686 B CN113506686 B CN 113506686B
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capacitor
mxene
substrate
film
polymer
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CN113506686A (en
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沈国震
许小寒
陈娣
李腊
胡楚乔
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Institute of Semiconductors of CAS
University of Science and Technology Beijing USTB
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Institute of Semiconductors of CAS
University of Science and Technology Beijing USTB
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The present disclosure discloses a thermal charging type capacitor and a method for manufacturing the same, wherein the thermal charging type capacitor includes: two electrode plates; a polymer solid electrolyte positioned between the two electrode sheets; the electrode plate comprises a substrate, and an MXene thin film and a 3-hexylthiophene polymer thin film which are sequentially coated on the substrate.

Description

Thermal charging type capacitor and preparation method thereof
Technical Field
The disclosure relates to the technical field of preparation of new energy materials and devices, in particular to a thermal charging type capacitor and a preparation method thereof.
Background
With the rapid growth of the global population and the development of the global economy, the contact between human beings is more and more close, and the demand of energy sources is exponentially increased. The crisis of energy shortage is a major problem that human beings have faced and will face for a long time since the recent times, and it is concerned with aspects of human survival and development. Therefore, human beings have been invested in much effort and thinking to develop, explore and utilize new sustainable renewable energy sources such as solar energy, hydro energy, wind energy, tidal energy, etc. Meanwhile, the development of efficient, stable and safe energy storage and conversion devices to realize sustainable utilization of energy is a research direction in which people need to make continuous effort and development in the future, and is also a hot frontier field in which numerous scientific researchers participate at home and abroad. The super capacitor is an important component of the existing energy storage device, and because of a series of advantages of high power density, high charging and discharging speed, long cycle life and the like, the super capacitor makes up for the short plates of the traditional parallel plate capacitor and battery, and is rapidly developed and applied. However, few studies have been conducted by researchers in the field of supercapacitors based on thermoelectric charging.
The super capacitor charged by temperature difference is designed and prepared by utilizing thermoelectric materials, and can generate potential difference in the materials through temperature gradient so as to supply power for other equipment. The thermoelectric material converts energy in a carrier or proton transport mode and does not consume fossil fuel, so the thermoelectric material has important application prospect in the aspects of reducing greenhouse gases and providing clean energy.
However, although there is a certain amount of research on the thermal charging type capacitor, the research is still blank in the field of the thermal charging type capacitor, and it is necessary to develop a thermal charging type capacitor to further meet the needs of production and living.
Disclosure of Invention
Technical problem to be solved
In view of the above technical problems, the present disclosure provides a rechargeable supercapacitor and a method for manufacturing the same to at least partially solve the above technical problems.
(II) technical scheme
In order to solve the technical problem, the technical scheme of the disclosure is as follows:
as an aspect of the present disclosure, there is provided a thermal charging type capacitor including:
two electrode plates;
a polymer solid electrolyte positioned between the two electrode sheets;
the electrode plate comprises a substrate, and an MXene thin film and a 3-hexylthiophene polymer thin film which are sequentially coated on the substrate.
In one embodiment, the substrate is made of a flexible material.
In one embodiment, the MXene film has a thickness of 20 μm to 50 μm;
the thickness of the 3-hexylthiophene polymer film is 5-10 mu m;
the thickness of the polymer solid electrolyte is 300-500 μm.
In one embodiment, the MXene film adopts Ti 3 C 2 Tx material.
As another aspect of the present disclosure, there is provided a method for manufacturing the above-described thermal charging type capacitor, comprising:
(1) Preparing an electrode plate: firstly, cleaning a substrate and carrying out plasma treatment; then, spraying the MXene dispersion liquid on the substrate to form an MXene film; finally, dissolving the 3-hexylthiophene polymer to form a 3-hexylthiophene polymer solution, and coating the 3-hexylthiophene polymer solution on the surface of the MXene film to form a 3-hexylthiophene polymer film, thereby forming an electrode slice;
(2) Preparing a capacitor: and (2) placing a polymer solid electrolyte between the two electrode plates in the step (1) in a heating state to form a capacitor.
In one embodiment, in the step (1), the concentration of the MXene dispersion is 2-10mg/mL.
In one embodiment, in the step (1), an MXene dispersion liquid is sprayed on the substrate by using a spray pen; wherein the distance between the spray pen and the substrate is 5-15cm.
In one embodiment, in the step (1), the concentration of the 3-hexylthiophene polymer solution is 0.8 to 1mg/mL.
In one embodiment, the MXene dispersion adopts Ti 3 C 2 Tx nanosheet dispersion.
In one embodiment, the preparation method of the polymer solid electrolyte comprises the following steps:
sequentially adding polyoxyethylene, lithium bistrifluoromethanesulfonimide and a polyvinylidene fluoride-hexafluoropropylene copolymer into N, N-dimethylacetamide according to a weight ratio of 2: 1: 0.1-0.2; then stirring and reacting for 2-4h at 50-60 ℃; and then transferring the electrolyte into a mold and drying for 12-24h to obtain the polymer solid electrolyte.
(III) advantageous effects
1. The capacitor provided by the disclosure adopts the MXene film and the 3-hexylthiophene polymer film to be compounded as the electrodes, and the two films are in cooperative action, so that more protons can be provided, the protons can be diffused to the cold end under the condition of temperature difference, the potential difference can be improved, and the potential difference of hundreds millivolt level can be generated under the condition of only temperature difference, so that other equipment can be charged. In addition, the capacitor in the disclosure supplies power to equipment through temperature difference, does not consume fossil fuel, and has important application prospect in the aspects of reducing greenhouse gas and providing clean energy
2. The capacitor provided by the disclosure is high in charging speed, safe, convenient and fast, and can be carried about.
Drawings
Fig. 1 is a schematic structural diagram of a thermal charging type capacitor of the present disclosure.
Fig. 2 is a cyclic voltammogram when a temperature difference exists between two electrode sheets of the thermal charging type capacitor of the present disclosure.
Fig. 3 is a graph comparing the mass ratio and the capacitance value when there is no temperature difference between two electrode plates and the temperature difference is 6.8 ℃.
Fig. 4 is an electrochemical performance test chart of the thermal charging type capacitor of the present disclosure when there is no temperature difference between two electrode sheets and the temperature difference is 6.8 ℃; fig. 4 (a) is a cyclic voltammogram, and fig. 4 (b) is a constant current charge and discharge curve.
Fig. 5 is a cyclic voltammogram of the two electrode sheets of the thermal charging capacitor of the present disclosure when different temperature differences are applied.
Fig. 6 is a graph of potential difference generated when different temperature differences are applied to two electrode sheets of the thermal charging type capacitor of the present disclosure.
FIG. 7 is a graph of the response of a thermally-charged capacitor-driven PtTe/Si heterojunction photodetector of the present disclosure; fig. 7 (a) is a response curve of the capacitor-driven photodetector when a temperature difference of 4.3 ℃ is applied between the two electrode sheets, and fig. 7 (b) is a response curve of the photodetector when a voltage of 30mV is directly applied across the photodetector.
Reference numerals are as follows: 1. a substrate; 2. MXene film; 3. a 3-hexylthiophene polymer film; 4. a polymer solid electrolyte.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
The present disclosure relates to a thermal charging type capacitor, including:
two electrode plates;
a polymer solid electrolyte positioned between the two electrode sheets;
the electrode plate comprises a substrate, and an MXene film and a 3-hexylthiophene polymer film which are sequentially coated on the substrate.
MXene is a two-dimensional inorganic compound composed of a transition metal carbide, nitride or carbonitride of several atomic layer thicknesses, thereby having the metallic conductivity of the transition metal carbide. MXene class of materials having multiple components (e.g., ti) 2 CTx、Ti 3 C 2 Tx、V 2 CTx and Nb 2 CTx, where T represents a surface termination group, such as F, cl, O or OH, has a large current charge and high conductivity (10) 3 -10 5 S/cm) and the stacked layered structure can be used for ion intercalation. Has good application prospect in the aspects of electrochemical energy storage, electromagnetic shielding, electrocatalysis, pressure sensors and the like.
In addition, MXene can provide protons due to the hydroxyl functional group, so that the protons can be diffused to the cold end in the presence of a temperature difference, and the potential difference can be improved.
The 3-hexylthiophene polymer (P3 HT) has a two-dimensional structure different from that of a common polymer, and is a good conductive polymer material. The conjugated structure contained in the molecular chain can provide electrons, so that the possibility of electric conduction is provided for the molecular chain; secondly, the molecular chain contains a large number of thiophene ring planar structures, so that the molecular chain has higher planar regularity, and accumulation of electrons among the molecular chains is facilitated. Compared with other organic thermoelectric materials, the 3-hexylthiophene polymer has good environmental stability and processability, and has a higher Seebeck coefficient in an undoped state.
However, for P3HT materials, when the conductivity is less than 10 -2 The Seebeck coefficient is as high as 1000. Mu.V/K at S/cm, but it rapidly decreases with an increase in conductivity, so that when the Seebeck coefficient of P3HT is high, the conductivity thereof decreases. In the disclosure, an MXene material and a P3HT material are compounded, and by utilizing the high Seebeck coefficient of the P3HT and the high electrical conductivity of the MXene, the electrical conductivity and the Seebeck coefficient of the compounded material are both greatly improved, while the thermal conductivity of the composite material is still maintained at a relatively low level, so that the thermoelectric property of the composite material is greatly enhanced.
Therefore, the capacitor provided by the disclosure can provide more protons by adopting the MXene film and the P3HT film as the electrodes in a compounding manner and the two films are in cooperative action, and the protons can be diffused to the cold end under the condition of temperature difference, so that the potential difference is improved, and therefore, the potential difference of hundreds of millivolts can be generated under the condition of only temperature difference, and other equipment can be charged. In addition, the capacitor in the disclosure supplies power to the equipment through temperature difference, does not consume fossil fuel, and has important application prospects in the aspects of reducing greenhouse gases and providing clean energy.
In addition, the capacitor that this disclosure provided, not only the charging speed is fast, and is safe convenient moreover to can hand-carry.
In one embodiment, the substrate is made of a flexible material.
In one embodiment, the substrate is made of polyethylene terephthalate (PET).
In one embodiment, the substrate is sized as a rectangle 5-10mm on a side.
The substrate disclosed by the invention is made of flexible materials such as polyethylene terephthalate and the like, can still normally work under the condition of generating certain deformation, and has great application potential in the aspect of wearable equipment.
In one embodiment, the MXene film has a thickness of 20 μm to 50 μm.
In one embodiment, for example, the MXene film may have a thickness of 20 μm, 30 μm, 40 μm, 50 μm, or the like.
In one embodiment, the thickness of the 3-hexylthiophene polymer film is 5 μm to 10 μm.
In one embodiment, for example, the 3-hexylthiophene polymer film may have a thickness of 5 μm, 8 μm, 10 μm, or the like.
In one embodiment, the polymer solid electrolyte has a thickness of 300 μm to 500 μm.
In one embodiment, for example, the polymer solid electrolyte may have a thickness of 300 μm, 400 μm, 500 μm, or the like.
In one embodiment, the MXene film adopts Ti 3 C 2 Tx material.
As another aspect of the present disclosure, there is provided a method for manufacturing the above-described thermal charging type capacitor, including:
(1) Preparing an electrode slice: firstly, cleaning a substrate and carrying out plasma treatment; then, spraying the MXene dispersion liquid on a substrate to form an MXene film; finally, dissolving the 3-hexylthiophene polymer to form a 3-hexylthiophene polymer solution, and coating the 3-hexylthiophene polymer solution on the surface of the MXene film to form a 3-hexylthiophene polymer film, thereby forming an electrode slice;
(2) Preparing a capacitor: and (3) placing the polymer solid electrolyte between the two electrode plates in the step (1) in a heating state to form a capacitor.
In the actual operation process of the preparation method provided by the disclosure, firstly, the polymer solid electrolyte is dried and cut into a required size, and when the capacitor is assembled, the polymer solid electrolyte is directly placed between two electrode plates and is bonded with the electrode plates through heating. Compared with the method of dripping the liquid electrolyte on the electrode plate, the preparation method disclosed by the disclosure is simple and convenient, not only saves time, but also can ensure that the polymer solid electrolyte has uniform thickness, and the problem that the middle part is thick and the two sides are thin is avoided.
In one embodiment, in step (1), the substrate is made of polyethylene terephthalate (PET).
In one embodiment, in the step (1), the substrate is respectively cleaned in ethanol and deionized water, and after being dried by blowing, plasma treatment is carried out; wherein the cleaning process is performed at least twice, each for 20min.
In one embodiment, the concentration of MXene dispersion in step (1) is 2-10mg/mL.
In one embodiment, in step (1), for example, the concentration of MXene dispersion may be 2mg/mL, 5mg/mL, 10mg/mL, or the like.
In one embodiment, in the step (1), the MXene dispersion liquid adopts Ti 3 C 2 Tx nanosheet dispersion.
In one embodiment, ti 3 C 2 The Tx nanosheet dispersion was prepared using the following method:
firstly, dissolving lithium fluoride in hydrochloric acid, and stirring for 0.5-1h to obtain a mixed solution, wherein the weight fraction of the lithium fluoride in the mixed solution is 8-12wt%; then Ti is slowly added to the mixed solution 3 AlC 2 (MAX phase), magnetically stirring for at least 24h, and performing etching process to obtain reaction solution, wherein Ti is 3 AlC 2 The adding amount of the lithium fluoride is 60 to 65 percent of the weight of the lithium fluoride; finally, washing the reaction solution with ultrapure water and centrifuging, wherein the centrifugal speed is set to 3500rpm/min, each time is 5min, repeatedly washing and centrifuging for 4-8 times, and collecting the supernatant when the pH value of the supernatant is more than or equal to 7, wherein the supernatant is Ti 3 C 2 Tx nanosheet dispersion, ti 3 C 2 The concentration of the Tx nanosheet dispersion is 2-10mg/mL.
Ti prepared by the method 3 C 2 The Tx nanosheet dispersion generates hydrofluoric acid through in-situ reaction of lithium fluoride and hydrochloric acid, the hydrofluoric acid is not directly used, and the preparation method is safe and environment-friendly.
In one embodiment, in the step (1), MXene dispersion liquid is sprayed on the substrate by using a spray pen; wherein the distance between the spray pen and the substrate is 5-15cm.
The MXene film prepared by spraying with the spray pen can form a layer of compact ultrathin film on the surface of the substrate, so that the material is saved, and the contact resistance can be reduced.
In one embodiment, in step (1), the concentration of the 3-hexylthiophene polymer solution is 0.8-1mg/mL.
In one embodiment, a method for preparing a polymer solid electrolyte includes:
sequentially adding polyoxyethylene, lithium bistrifluoromethanesulfonimide and a polyvinylidene fluoride-hexafluoropropylene copolymer into N, N-dimethylacetamide according to a weight ratio of 2: 1: 0.1-0.2; then stirring and reacting for 2-4h at 50-60 ℃; then transferring the mixture into a mold and drying for 12-24h to obtain the polymer solid electrolyte.
The polymer solid electrolyte in the disclosure is prepared by polyethylene oxide, and polyethylene oxide can provide protons to be matched with an MXene film and a 3-hexylthiophene polymer film, so that the potential difference of the capacitor is further improved. Furthermore, polyethylene oxide is also excellent in thermal stability.
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments and the accompanying drawings.
Fig. 1 is a schematic structural diagram of a thermal charging type capacitor of the present disclosure.
Referring to fig. 1, the present embodiment discloses a thermal charging type capacitor including two electrode sheets and a polymer solid electrolyte 4 disposed between the electrode sheets; the electrode plate comprises a substrate 1, an MXene thin film 2 and a 3-hexylthiophene polymer thin film 3, wherein the substrate 1 is a rectangular thin sheet made of PET materials, and the substrate 1 is a square with the thickness of 7 multiplied by 7 mm. An MXene film 2 is coated on one side of the substrate 1 close to the polymer solid electrolyte 4, and the MXene film 2 adopts Ti 3 C 2 Tx nanosheet dispersion was spray formed and the MXene film 2 had a thickness of 20 μm. The 3-hexylthiophene polymer film 3 is coated on the MXene film 2 and is formed by coating a 3-hexylthiophene polymer solution, and the thickness of the 3-hexylthiophene polymer film 3 is 5 mu m.
The method for manufacturing the thermal charging capacitor comprises the following steps:
(1) Preparing an electrode slice:
cleaning of PET substrate: cutting a PET substrate into 2 multiplied by 2cm, respectively ultrasonically cleaning in ethanol and deionized water for 20min, blow-drying by using an air gun, and then putting into a plasma cleaning machine for glow cleaning for 5min;
b, preparing MXene films: mixing Ti 3 C 2 Injecting Tx nanosheet dispersion into a liquid gun of an art spray pen, and controlling the distance between the art spray pen and a PET substrate to be 10cm so that Ti is formed 3 C 2 Uniformly spraying the Tx nanosheet dispersion on a PET substrate, and drying to form Ti with the thickness of 20 mu m 3 C 2 A Tx film.
Wherein, ti 3 C 2 The preparation method of the Tx nanosheet dispersion is as follows:
firstly, dissolving 1.6g of lithium fluoride in 15mL of hydrochloric acid, and stirring for 30min to obtain a mixed solution; then, 1g of Ti was slowly added to the mixed solution 3 AlC 2 Magnetically stirring for 24 hours, and etching to obtain reaction liquid; then washing the reaction solution with ultrapure water, centrifuging at 3500rpm/min for 5min each time, repeatedly washing and centrifuging for 4-8 times to make the pH value of the supernatant be greater than or equal to 7, and collecting the supernatant, which is Ti 3 C 2 Tx nanosheet dispersion. Taking out a fixed amount of Ti 3 C 2 Vacuum filtering the Tx nanosheet dispersion, drying and weighing to obtain Ti 3 C 2 The concentration of the Tx nanosheet dispersion was 5mg/mL.
c, preparing a 3-hexylthiophene polymer film: dipping the 3-hexylthiophene polymer solution by using a brush pen, and coating the solution on Ti 3 C 2 Drying the surface of the Tx film to form a 3-hexylthiophene polymer film with the thickness of 5 mu m; will then be coated with Ti 3 C 2 The substrate of the Tx film and the 3-hexylthiophene polymer film was cut into a size of 5X 5mm to form an electrode sheet.
The preparation method of the 3-hexylthiophene polymer solution comprises the following steps: 1mg of 3-hexylthiophene polymer solid was added to 1mL of chlorobenzene solution, and stirred under a shade for 24 hours.
(2) Preparing a capacitor:
setting the temperature of a constant temperature heating table to be 60 ℃, firstly, placing one electrode plate on the constant temperature heating table, then placing the polymer solid electrolyte on the electrode plate, then placing the other electrode plate on the polymer solid electrolyte, and bonding the polymer solid electrolyte and the electrode plate by heating to form the capacitor.
The preparation method of the polymer solid electrolyte comprises the following steps:
first, 4g of polyethylene oxide (PEO), 2g of lithium bistrifluoromethanesulfonimide (LiTFSI), and 0.34g of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) were sequentially added to 50mL of N, N-dimethylacetamide (DMAc) and dissolved; then stirred at 55 ℃ for 3 hours to obtain a reaction solution, and finally the reactor was moved to a mold and vacuum-dried at 60 ℃ for 24 hours to obtain a polymer solid electrolyte having a thickness of 400 μm.
Electrochemical and thermoelectric performance tests were performed on the capacitors prepared using the above method to further illustrate the present disclosure.
The specific tests are as follows:
1. electrochemical performance test without temperature difference between two electrode plates
The positive electrode and the negative electrode of the electrochemical workstation are respectively clamped on two electrode sheets of the capacitor, and then the cyclic voltammetry test is carried out, wherein the test environment temperature is 25 ℃, and the test result is shown in figure 2.
As can be seen from fig. 2, the optimal voltage range of the thermal charging type capacitor of the present disclosure is 0 to 3V. Through tests of different voltage scanning rates (0.01V/s, 0.1V/s, 0.5V/s and 1V/s), the maximum mass ratio capacitance value under the condition of not applying temperature difference is 37F/g.
2. Mass ratio capacitance value test when there is no temperature difference between two electrode plates and the temperature difference is 6.8 DEG C
A heating plate and a Peltier are respectively attached to two electrode plates of the capacitor to control the temperature difference to be 6.8 ℃, and the mass ratio capacitance value of the capacitor is tested, and the test result is shown in figure 3.
As can be seen from fig. 3, when there is a temperature difference of 6.8 ℃ between the two electrode sheets, the mass ratio capacitance of the capacitor is 194F/g, which is greatly improved compared to 37F/g when no temperature difference (i.e., the curve represented by RT) is applied at room temperature, indicating that the existence of the temperature difference has a good effect on the electrochemical performance of the capacitor.
3. Electrochemical performance test without temperature difference between the two electrode plates and with the temperature difference of 6.8 DEG C
(1) Cyclic voltammetry test
A heating piece and a Peltier were attached to both electrode pieces of the capacitor, respectively, to control the temperature difference to 6.8 ℃, and then cyclic voltammetry was performed at a sweep rate of 10mV/s, and the results are shown in FIG. 4 (a).
As can be seen from fig. 4 (a), when the temperature difference between the two electrode sheets is 6.8 ℃, the area of the Cyclic Voltammetry (CV) graph is significantly larger than that of the graph without the temperature difference (i.e., the curve represented by RT), which indicates that the mass ratio and capacitance of the Wen Chashi capacitor are increased.
(2) Constant current charge and discharge test
A heating plate and a Peltier are respectively attached to two electrode plates of the capacitor to control the temperature difference to be 6.8 ℃, and a constant current charging and discharging test is carried out in a voltage window range of 0-3V, and the test result is shown in figure 4 (b).
As shown in fig. 4 (b), when the temperature difference of the capacitor is 6.8 ℃, the discharge time of the capacitor can reach 620 seconds, which is much longer than 370 seconds without the temperature difference (i.e. the curve represented by RT), and the capacitor shows excellent electrochemical performance.
4. Electrochemical performance test under different temperature difference applied between two electrode plates
(1) A heating plate and a Peltier are respectively attached to two electrode plates of the capacitor to control the temperature difference to be 4.3 ℃, 6.8 ℃, 9.4 ℃, 14.4 ℃ and 18 ℃, and then cyclic voltammetry tests are respectively carried out at a scanning rate of 10mV/S, and the test results are shown in FIG. 5.
As can be seen from fig. 5, the area of the CV diagram of the capacitor in the present disclosure increases as the temperature difference between the two electrode sheets increases, and the specific capacitance value of the capacitor in the present disclosure increases as the temperature difference increases.
5. Thermoelectric performance test when different temperature differences are applied between two electrode plates
The results of measuring the potential difference of the capacitor by attaching a heating sheet and a peltier element to the two electrode sheets of the capacitor to control the temperature difference to be 4.3 c, 6.8 c, 9.4 c, 14.4 c, and 18 c, respectively, are shown in fig. 6.
As can be seen from fig. 6, when the temperature difference between the two electrode sheets is 4.3 ℃, 6.8 ℃, 9.4 ℃, 14.4 ℃ and 18 ℃, the potential difference generated within 250 seconds is 40mV, 85mV, 120mV, 145mV and 180mV, respectively, which indicates that the capacitor of the present disclosure can generate considerable potential difference within the temperature difference range within 20 ℃, and thus it is possible to supply power to other devices using the temperature difference. In addition, as can be seen from fig. 6, when the cold and hot ends of the capacitor are changed, the potential difference also becomes a negative value accordingly.
6. Temperature differential drive testing of capacitors
Applying a temperature difference of 4.3 ℃ between the two electrode plates to enable the capacitor to generate a thermoelectric potential; then, the temperature difference between the two electrode sheets is removed, the PtTe/Si heterojunction photodetector is charged with a temperature difference potential generated by a capacitor, and the response curve of the PtTe/Si heterojunction photodetector driven by the temperature difference is shown in fig. 7 (a).
The response curve when a voltage of 30mV was applied directly across the photodetector is shown in FIG. 7 (b).
As can be seen from fig. 7 (a) and 7 (b), the magnitude of the current response when a temperature difference of 4.3 ℃ is applied between the two electrode plates is the same magnitude as the magnitude of the current response when a voltage of 30mV is directly applied between the two electrode plates, which means that the capacitor in the present disclosure can generate a potential difference through the temperature difference to charge the capacitor, and the capacitor can charge other devices after the temperature difference is removed, that is, the capacitor in the present disclosure can successfully supply power to other devices.
The above-described embodiments, objects, technical solutions and advantages of the present disclosure are further described in detail, it should be understood that the above-described embodiments are only examples of the present disclosure, and should not be construed as limiting the present disclosure, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.

Claims (10)

1. A thermally-chargeable capacitor, comprising:
two electrode plates;
a polymer solid electrolyte positioned between the two electrode sheets;
the electrode plate comprises a substrate, and an MXene thin film and a 3-hexylthiophene polymer thin film which are sequentially coated on the substrate;
the thickness of the MXene film is 20-50 μm;
the thickness of the 3-hexylthiophene polymer film is 5-10 mu m.
2. The thermally-chargeable capacitor of claim 1,
the substrate is made of flexible materials.
3. The thermally-chargeable capacitor of claim 1,
the thickness of the polymer solid electrolyte is 300-500 μm.
4. The thermally-chargeable capacitor of claim 1,
the MXene film adopts Ti 3 C 2 Tx material.
5. A method for manufacturing a thermal charging type capacitor as claimed in any one of claims 1 to 4, comprising:
(1) Preparing an electrode slice: firstly, cleaning a substrate and carrying out plasma treatment; then, spraying the MXene dispersion liquid on the substrate to form an MXene film; finally, dissolving the 3-hexylthiophene polymer to form a 3-hexylthiophene polymer solution, and coating the 3-hexylthiophene polymer solution on the surface of the MXene film to form a 3-hexylthiophene polymer film, thereby forming an electrode slice;
(2) Preparing a capacitor: and (2) placing a polymer solid electrolyte between the two electrode plates in the step (1) in a heating state to form a capacitor.
6. The method for manufacturing a heat-charging type capacitor according to claim 5,
in the step (1), the concentration of the MXene dispersion liquid is 2-10mg/mL.
7. The method for manufacturing a heat-charging type capacitor according to claim 5,
in the step (1), spraying MXene dispersion liquid on the substrate by using a spray pen; wherein the distance between the spray pen and the substrate is 5-15cm.
8. The method for producing a thermally chargeable capacitor as claimed in claim 5,
in the step (1), the concentration of the 3-hexylthiophene polymer solution is 0.8-1mg/mL.
9. The method for manufacturing a heat-charging type capacitor according to claim 5,
the MXene dispersion liquid adopts Ti 3 C 2 Tx nanosheet dispersion.
10. The method for manufacturing a heat-charging type capacitor according to claim 5,
the preparation method of the polymer solid electrolyte comprises the following steps:
sequentially adding polyoxyethylene, lithium bistrifluoromethanesulfonylimide and polyvinylidene fluoride-hexafluoropropylene copolymer into N, N-dimethylacetamide according to the weight ratio of 2: 1: 0.1-0.2; then stirring and reacting for 2-4h at 50-60 ℃; then transferring the mixture into a mold and drying for 12-24h to obtain the polymer solid electrolyte.
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