CN114242466A - Super capacitor with electrochromic function and high energy density and preparation method thereof - Google Patents
Super capacitor with electrochromic function and high energy density and preparation method thereof Download PDFInfo
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- CN114242466A CN114242466A CN202111578579.6A CN202111578579A CN114242466A CN 114242466 A CN114242466 A CN 114242466A CN 202111578579 A CN202111578579 A CN 202111578579A CN 114242466 A CN114242466 A CN 114242466A
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Images
Classifications
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors 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
- H01G11/26—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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention relates to a super capacitor with electrochromic function and high energy density and a preparation method thereof, wherein the super capacitor comprises a negative current collector, a negative energy storage electrode layer, an electrolyte, a positive energy storage electrode layer and a positive current collector from top to bottom in sequence; the negative current collector comprises a transparent substrate, an electrochromic layer and a conductive metal layer from top to bottom; the transparent substrate allows part or all of visible light to penetrate through; the electrochromic layer can realize different color changes under electrochemical stimulation; the conductive metal layer can reflect part or all visible light and has a porous structure penetrating through the upper surface and the lower surface, and ions in the electrolyte can penetrate through the porous structure of the conductive metal layer to be in contact with the electrochromic layer in the charge and discharge process of the supercapacitor, so that the negative current collector has an electrochromic function. The negative current collector is in a reflection type electrochromic mode, and the problem that a super capacitor in the prior art cannot have the functions of high energy density and electrochromic is solved.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a super capacitor with an electrochromic function and high energy density and a preparation method thereof.
Background
The super capacitor is a novel electrochemical energy storage device with higher power density and energy density than the traditional battery, and provides an energy supply mode with balanced power and energy for electronic products. The electrochromic function is integrated in the super capacitor, so that the state of residual energy can be judged by observing the appearance color change of the super capacitor through human eyes, and the energy visualization function is convenient for people to monitor and manage the energy of the super capacitor at any time. The electrochromic process does not need extra signal detection, processing and feedback circuit or original paper, is more favorable to the miniaturization and the lightweight development of electronic products, is particularly suitable for multi-functional intelligent wearable electronic products.
At present, an electrochromic-supercapacitor with an energy visualization function is generally designed to be fully transparent and comprises a transparent current collector, a transparent electrode material and a transparent electrolyte, and the supercapacitor generates different color information by adjusting the light transmittance of transmitted light in an electrochemical reaction process so as to correspond to the internal energy state of the supercapacitor. The transparent electrode material plays a dual role of electrochromism and energy storage in the charge and discharge processes of the super capacitor, and due to the transparency design requirement of the electrode material during electrochromism, the electrode material must be made very thin, usually less than 200nm, so that the load capacity of the electrode material is limited, and the energy density of the super capacitor is further limited. The energy density of the current electrochromic supercapacitor is usually 1-2 orders of magnitude lower than that of a conventional supercapacitor with a single energy storage function, and the development and practical application of the electrochromic supercapacitor to a wearable power supply are hindered due to the huge difference in energy density. The simplest and most straightforward way to increase the energy density of an electrochromic-supercapacitor is to increase the loading of the electrode material, which would result in a significant reduction in the transparency of the supercapacitor, even if the supercapacitor loses its electrochromic energy visualization function. At present, the existing electrochromic-super capacitor cannot keep a good energy visualization function under the condition that the energy density is remarkably increased, and the existing electrochromic-super capacitor is usually designed to be fully transparent, so that the background color information of the electrochromic-super capacitor is mixed with the color information generated by the electrochromic of the super capacitor in the actual working process, the color information generated by the electrochromic of the super capacitor is difficult to observe, and the accuracy of identifying the internal energy of the super capacitor is remarkably reduced.
In addition, as an important component of the supercapacitor, the design of the current collector has an important influence on the performance, the manufacturing cost and the application range of the supercapacitor. At present, a current collector used in a super capacitor is made of metal foil, carbon film material or conductive glass, and the like, and only has common functions of mechanical support and electric conduction. Conductive glass (including ITO and FTO) is used as the most commonly used current collector material for electrochromic-supercapacitors due to its good transparency to visible light and well-established commercial production processes. However, the conductivity of the conductive glass is 1 to 3 orders of magnitude lower than that of the conventional current collector represented by a metal foil or a carbon film material, which aggravates the resistance of electron transmission in an electrode material and further limits the electrochemical performance of the supercapacitor. Although the use of a non-transparent current collector with higher conductivity can generally promote the energy storage performance of a supercapacitor, the prior art has not realized the integration of a non-transparent current collector with the electrochromic function of a supercapacitor.
In view of this, the present application designs a super capacitor having both an electrochromic function and a high energy density, which does not require full transparency of the super capacitor on the premise of implementing the electrochromic function, and has a high energy density.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a super capacitor with electrochromic function and high energy density and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the super capacitor is characterized in that the super capacitor sequentially comprises a negative current collector, a negative energy storage electrode layer, an electrolyte, a positive energy storage electrode layer and a positive current collector from top to bottom;
the negative current collector comprises a transparent substrate, an electrochromic layer and a conductive metal layer from top to bottom; the transparent substrate allows part or all of visible light to penetrate through; the electrochromic layer can realize different color changes under electrochemical stimulation; the conductive metal layer can reflect part or all visible light and has a porous structure penetrating through the upper surface and the lower surface, and ions in the electrolyte can penetrate through the porous structure of the conductive metal layer to be in contact with the electrochromic layer in the charge and discharge process of the supercapacitor, so that the negative current collector has an electrochromic function.
The lower surface of the electrochromic layer has surface roughness, and the conductive metal is deposited on the lower surface of the electrochromic layer through physical vapor deposition to form a conductive metal layer.
The transparent substrate is made of common glass, conductive glass or a PET flexible film, and the thickness of the transparent substrate is 30-10000 microns.
The electrochromic layer is made of polypyrrole and grows on the lower surface of the transparent substrate in a chemical polymerization mode; the thickness of the electrochromic layer is 50-1000 nm.
The conductive metal layer is made of silver, aluminum, copper or gold, and the thickness of the conductive metal layer is 50-6000 nm.
The negative energy storage electrode layer takes a molybdenum oxide nanobelt as a main body material, and carbon nanotubes are mixed in the molybdenum oxide nanobelt, so that the negative energy storage electrode layer has a large number of pores.
The positive energy storage electrode layer is made of manganese dioxide nanoparticles.
The positive current collector is made of aluminum foil, titanium foil, carbon material films, ITO/Glass conductive Glass or ITO/PET flexible conductive films.
The invention also provides a preparation method of the super capacitor with electrochromic function and high energy density, which is characterized by comprising the following steps:
1) preparing a negative energy storage electrode material:
adding 1g of molybdenum metal powder into 5mL of deionized water to form uniformly dispersed suspension; then, slowly adding 20mL of hydrogen peroxide solution with the mass fraction of 30% into the suspension, and continuously stirring for 30min to obtain a suspension after reaction; transferring the suspension after the reaction into a stainless steel autoclave with polytetrafluoroethylene as an inner liner, and heating to 220 ℃ for 72 hours to obtain white precipitate; washing the white precipitate for several times by using deionized water to obtain molybdenum oxide powder; finally, vacuum drying the molybdenum oxide powder at 60 ℃ for 8h to obtain a molybdenum oxide nanobelt; mixing the molybdenum oxide nanobelt and the carbon nanotube according to the mass ratio of 9:1, and uniformly mixing by mechanical grinding to obtain a negative energy storage electrode material;
2) preparing a positive energy storage electrode material:
dissolving 0.3g of potassium permanganate in 30mL of deionized water, and continuously stirring for 30min at room temperature until the potassium permanganate is completely dissolved; adding 0.05g of glucose into the solution to reduce potassium permanganate, and stirring for 12 hours; then, centrifugally cleaning for 3 times by using deionized water, and drying for 6 hours at 60 ℃ to obtain manganese dioxide nanoparticles;
3) preparing a negative current collector:
cleaning of Step1 transparent substrate: preparing a transparent substrate by using common glass, placing the glass with the thickness of 2mm in deionized water for ultrasonic cleaning for 20min, then transferring the glass into absolute ethyl alcohol for ultrasonic cleaning for 20min, and finally placing the glass in a blast drying oven at 60 ℃ for drying for later use;
step2 growth of electrochromic layer: 150mL of polypyrrole polymerization growth solution is filled in a reaction container, the cleaned and dried glass is placed in the polypyrrole polymerization growth solution, the glass is placed perpendicular to the bottom of a beaker and is completely immersed in the polypyrrole polymerization growth solution, the glass is taken out of the polypyrrole polymerization growth solution after reaction for 70min, a large amount of deionized water and ethanol are used for washing for a plurality of times, drying is carried out for 30min at 60 ℃, polypyrrole films, namely electrochromic layers, are formed on the upper surface and the lower surface of the conductive glass, and then the polypyrrole films on the upper surface of the conductive glass are wiped off by using a cotton swab dipped with N, N-dimethylformamide, so that the growth of the electrochromic layers is completed;
step3 depositing a conductive metal layer: selecting Ag as the conductive metal, transferring the glass with the polypyrrole film obtained in Step2 into an evaporation machine, and enabling one side of the glass with the polypyrrole film to face an Ag evaporation source; in the evaporation process, the distance between the polypyrrole film and the Ag evaporation source is fixed to be 50cm, the polypyrrole film is kept rotating at the speed of 20r/min, and the pressure in the working chamber of the evaporation machine is kept to be 2.4 multiplied by 10-4Pa or less, the evaporation rate being maintained at
Finally, plating a silver film, namely a conductive metal layer, on the lower surface of the electrochromic layer to finish the preparation of the negative current collector;
4) assembling the super capacitor:
firstly, respectively mixing and stirring 85 wt% of anode energy storage electrode material and cathode energy storage electrode material, 10 wt% of acetylene black and 5 wt% of 1-methyl-2-pyrrolidone solvent for 6 hours to form anode energy storage electrode slurry and cathode energy storage electrode slurry; respectively coating the anode energy storage electrode slurry and the cathode energy storage electrode slurry on the upper surface of an anode current collector and the lower surface of a cathode current collector by scraping, and drying at 80 ℃ for 12h to form an anode energy storage electrode layer and a cathode energy storage electrode layer; the positive current collector adopts ITO/Glass conductive Glass; the positive energy storage electrode layer and the positive current collector form a positive electrode of the super capacitor, the negative energy storage electrode layer and the negative current collector form a negative electrode of the super capacitor, then the hollow PDMS frame is placed between the positive electrode and the negative electrode of the super capacitor to be used as a diaphragm, and LiClO with the concentration of 1mol/L is injected by using an injector4Injecting the aqueous solution into the PDMS frame clip as an electrolyte; finally, the whole super capacitor is sealed by waterproof silica gel to complete the super capacitorAnd (4) assembling the container.
Compared with the prior art, the invention has the beneficial effects that:
1. the negative current collector adopts a layered structure design and comprises a transparent substrate, an electrochromic layer and a conductive metal layer, wherein the electrochromic layer presents different color changes in the charging and discharging processes of the super capacitor, visible light is reflected on the surface of the conductive metal layer after penetrating through the transparent substrate, the reflective electrochromism of the negative current collector is realized, the energy of the super capacitor is visualized, the defect that the current collector of the existing super capacitor has a single function is overcome, and the problem that the electrochromism function of the super capacitor cannot be realized by using a non-transparent current collector with better conductivity in the prior art is solved.
2. Because the negative current collector has an electrochromic function and does not require the energy storage electrode layer to have the electrochromic function at the same time, the application allows various high-performance supercapacitor materials to be used as energy storage electrode materials, so that the selection range of the energy storage electrode materials is greatly widened, and some energy storage electrode materials (such as carbon nano materials) with higher performance and lower cost can be used, so that the energy storage performance of the supercapacitor is improved and the production cost is reduced.
3. Different with realizing ultracapacitor system (full transparent ultracapacitor system) electrochromic through the transmitted light among the prior art, the ultracapacitor system of this application realizes electrochromic through the reverberation, consequently does not need the ultracapacitor system to be made full transparent, and the colour that the ultracapacitor system electrochromic produced is difficult for producing with environment background colour and confuses, is favorable to judging ultracapacitor system internal energy state more accurately, has solved full transparent ultracapacitor system and has observed the not high problem of colour discernment internal energy state accuracy through people's eye.
4. The super capacitor provided by the invention not only has an electrochromic function, but also allows more energy storage electrode materials to be loaded, namely, the thickness of an energy storage electrode layer is allowed to be thicker, so that a single super capacitor realizes larger area specific capacitance and energy density, the electrochemical energy storage capacity of the super capacitor is greatly enhanced, and the electrochromic function of the super capacitor is reserved.
Drawings
FIG. 1 is a schematic diagram of the construction of an ultracapacitor of the present invention;
fig. 2 is a flow chart of the present invention for preparing a negative electrode current collector;
FIG. 3(a) is a scanning electron microscope image of a polypyrrole film made according to the invention;
FIG. 3(b) is a scanning electron microscope image of a silver thin film prepared according to the present invention;
FIG. 3(c) is a high scanning electron microscope image of a silver thin film prepared according to the present invention;
fig. 4(a) is an electrochemical in-situ visible light reflection spectrum test result of the negative electrode current collector prepared according to the present invention;
fig. 4(b) is an electrochromic efficiency test result of the negative electrode current collector prepared according to the present invention;
fig. 4(c) is an electrochromic switching time test result of the negative electrode current collector prepared according to the present invention;
fig. 4(d) is an electrochromic cycle stability test result of the negative current collector prepared in the present invention;
FIG. 5(a) is the result of cyclic voltammetry testing of a supercapacitor made according to the present invention;
FIG. 5(b) shows the charge and discharge test results of the super capacitor prepared according to the present invention under different constant current densities;
fig. 5(c) is a real-time change of the reflectivity of the negative current collector to visible light with a wavelength of 650nm when the charging and discharging voltage of the supercapacitor prepared by the invention changes;
fig. 5(d) is a real-time variation of brightness and chromaticity of the appearance color of the negative current collector of the super capacitor prepared by the invention under voltages corresponding to different energy states;
FIG. 6(a) is the result of electrochemical energy storage stability test of the flexible supercapacitor prepared according to the present invention at different bending angles;
FIG. 6(b) is an energy visualization diagram of a flexible supercapacitor prepared by the invention in a bending state;
in the figure, 1-negative current collector; 2-a negative energy storage electrode layer; 3-an electrolyte; 4-a positive energy storage electrode layer; 5-positive current collector; 101-a transparent substrate; 102-an electrochromic layer; 103-conductive metal layer.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but the protection scope of the present invention is not limited thereto.
The invention relates to a super capacitor with electrochromic function and high energy density, which comprises a negative current collector 1, a negative energy storage electrode layer 2, an electrolyte 3, a positive energy storage electrode layer 4 and a positive current collector 5 from top to bottom in sequence as shown in figure 1;
the negative electrode current collector 1 comprises a transparent substrate 101, an electrochromic layer 102 and a conductive metal layer 103 from top to bottom; the transparent substrate 101 allows some or all visible light to pass through; the electrochromic layer 102 can realize macroscopic color change under electrochemical stimulation, so that the energy of the supercapacitor is visualized; the conductive metal layer 103 can reflect part or all of visible light and has a porous structure penetrating through the upper and lower surfaces, and ions in the electrolyte 3 can penetrate through the porous structure of the conductive metal layer 103 to contact the electrochromic layer 102, so that the negative electrode current collector 1 has an electrochromic function.
The transparent substrate 101 can allow part or all of visible light with the wavelength of 300nm to 800nm to penetrate through, and can be made of common glass, conductive glass or a PET (polyethylene terephthalate) flexible film and the like, so as to provide mechanical support for the electrochromic layer 102 and the conductive metal layer 103; the thickness of the transparent substrate 101 is 30 to 10000 μm.
The electrochromic layer 102 is made of a material with electrochromic property, for example, an organic conductive polymer polypyrrole which can perform macroscopic color conversion from black brown to yellow green under electrochemical stimulation, and shows different colors along with potential change in the charging and discharging processes of the supercapacitor; the electrochromic layer 102 has a thickness of 50 to 1000 nm.
The conductive metal layer 103 is made of conductive metals such as silver, aluminum, copper and gold, when visible light with a wavelength of 300nm to 800nm is radiated on the surface of the conductive metal layer 103, the conductive metal layer 103 can reflect part or all of the visible light, so that the reflective electrochromism of the negative current collector 1 is realized, and the conductive metal layer is used as a main conductive path of the negative current collector 1; the thickness of the conductive metal layer 103 is 50-6000 nm.
The transparent substrate 101, the electrochromic layer 102, and the conductive metal layer 103 are all in the form of thin films. The electrochromic layer 102 grows on the lower surface of the transparent substrate 101 in situ in a liquid-phase oxidation polymerization mode by adopting polypyrrole, and the electrochromic layer 102 and the transparent substrate 101 are connected by forming a large number of hydrogen bonds to realize interface connection so as to realize tight combination and improve contact strength; the lower surface of the electrochromic layer 102 has a certain surface roughness, which is a necessary condition for the conductive metal layer 103 to have porosity.
The conductive metal layer 103 is made of conductive metal and is coated on the lower surface of the electrochromic layer 102 by a thermal evaporation vapor deposition method to form a conductive metal film; since the lower surface of the electrochromic layer 102 has surface roughness, the conductive metal thin film can form a large number of porous deposition defects, i.e., a porous structure, due to a shadow effect during the thermal evaporation vapor deposition preparation process, and the porous structure can extend from the lower surface of the electrochromic layer 102 to the lower surface of the conductive metal layer 103, i.e., through the upper and lower surfaces of the conductive metal layer 103. During the charging and discharging process of the super capacitor, ions in the electrolyte 3 can penetrate through the negative energy storage electrode layer 2 to act on the negative current collector 1, and penetrate through the porous structure of the conductive metal layer 103 to contact with the electrochromic layer 102, so that electrochromic is initiated.
The negative energy storage electrode layer 2 is made of molybdenum oxide (MoO)3) The nanobelt is the main material in MoO3The Carbon Nanotubes (CNTs) are mixed in the carbon nanotubes, so that the conductivity of the negative energy storage electrode layer 2 is further improved, and the improvement of electrochemical performance is promoted. In addition, in MoO3During the mixing process of the nano-belt and the CNTs material, due to MoO3The nanobelt has a one-dimensional linear geometry, so that the negative energy storage electrode layer 2 has a large number of pores, which is beneficial for ions in the electrolyte 3 to penetrate through the negative energy storage electrode layer 2 and act on the negative current collector 1.
The front partManganese dioxide (MnO) is adopted as the electrode energy storage electrode layer 42) The nano particles are prepared, and have higher specific surface area and theoretical specific capacitance, so that a super capacitor can obtain larger energy storage capacity; MnO of2Anode energy storage electrode layer 4 made of nano particles and MoO3The negative energy storage electrode layer 2 taking the nanobelts as the main material is matched and assembled into an asymmetric super capacitor structure, so that a high voltage window of 1.8V is obtained, and the super capacitor has higher energy density.
And the load capacity of each square centimeter area of the positive energy storage electrode layer 4 and the negative energy storage electrode layer 2 on respective current collectors is more than 0.1 mg.
LiClO is selected as the electrolyte 34The concentration of the aqueous solution is 1mol/L, and the aqueous solution provides available ions for the energy storage and electrochromic processes of the super capacitor.
The positive current collector 5 can be made of aluminum foil, titanium foil, carbon material film, ITO/Glass conductive Glass or ITO/PET (polyethylene terephthalate) flexible conductive film, etc., and serves as a coating carrier of the positive energy storage electrode layer 4 and provides necessary conductivity for the electrochemical reaction process.
The super capacitor is assembled in the following way: the negative energy storage electrode layer 2 is coated on the lower surface of the conductive metal layer 103 of the negative current collector 1 to form a negative electrode of the super capacitor, the positive energy storage electrode layer 4 is coated on the upper surface of the positive current collector 5 to form a positive electrode of the super capacitor, the positive electrode and the negative electrode of the super capacitor are oppositely arranged at a spacing distance of 10-1000 microns, electrolyte 3 is filled between the positive electrode and the negative electrode, and packaging is carried out to prevent the electrolyte 3 from leaking.
The energy visualization of the super capacitor is realized by the way that the electrochromic layer 102 in the negative electrode current collector 1 displays different appearance colors when the energy in the super capacitor changes by utilizing the electrochromic effect of the electrochromic layer 102. When the super capacitor works actually, the upper surface of the negative current collector 1, namely the upper surface of the transparent substrate 101 faces a user; the lower surface of the negative current collector 1, i.e. the lower surface of the conductive metal layer 103, is coated with a negative energy storage electrode layer 2 to realize electrochemical energy storage of the supercapacitor. The principle of the super capacitor is as follows: visible light is incident from the upper surface of the transparent substrate 101 and penetrates through the transparent substrate 101 to act on the upper surface of the conductive metal layer 103, in the charging and discharging process of the supercapacitor, ions in the electrolyte 3 penetrate through the negative energy storage electrode layer 2 and the conductive metal layer 103 and are in contact with the electrochromic layer 102, so that the electrochromic layer 102 generates electrochromism and is reflected through the conductive metal layer 103, reflected light with colors penetrates through the transparent substrate 101 to enter human eyes, and the energy state inside the supercapacitor is sensed through the color change of the electrochromic layer 102.
The preparation method of the supercapacitor with the electrochromic function and the high energy density comprises the following steps:
1) preparing a negative energy storage electrode material:
adding 1g of molybdenum (Mo) metal powder into 5mL of deionized water to form uniformly dispersed suspension; then, slowly adding 20mL of hydrogen peroxide solution with the mass fraction of 30% into the suspension, and continuously stirring for 30min to ensure that the reaction is complete to obtain the suspension after the reaction; transferring the suspension after the reaction into a stainless steel autoclave with polytetrafluoroethylene as an inner liner, and heating to 220 ℃ for 72 hours to obtain white precipitate; washing the white precipitate with deionized water for several times, and washing salt by-product obtained in the chemical synthesis process to obtain MoO3Powder; finally, MoO is added3Vacuum drying the powder at 60 deg.C for 8h to obtain MoO3A nanoribbon; adding MoO3And mixing the nanobelts and the carbon nanotubes according to the mass ratio of 9:1, and uniformly mixing by mechanical grinding to obtain the negative energy storage electrode material.
2) Preparing a positive energy storage electrode material:
dissolving 0.3g of potassium permanganate in 30mL of deionized water, and continuously stirring for 30min at room temperature until the potassium permanganate is completely dissolved; adding 0.05g of glucose into the solution to reduce potassium permanganate, and stirring for 12 hours; then centrifugally cleaning for 3 times by using deionized water, and drying for 6 hours at 60 ℃ to obtain brown MnO2And (3) nanoparticles.
3) Preparation of negative current collector, see fig. 2:
cleaning of Step1 transparent substrate: preparing a transparent substrate by adopting common glass, placing the glass with the thickness of 2mm in deionized water, ultrasonically cleaning for 20min, then transferring the glass into absolute ethyl alcohol, ultrasonically cleaning for 20min, and finally placing the glass in a blast drying oven at 60 ℃ for drying for later use;
step2 growth of electrochromic layer: taking a 250mL beaker as a reaction container, filling 150mL of polypyrrole polymerization growth solution in the reaction container, putting cleaned and dried glass into the polypyrrole polymerization growth solution, enabling the glass to be placed perpendicular to the bottom of the beaker and completely immersed in the polypyrrole polymerization growth solution, taking the glass out of the polypyrrole polymerization growth solution after reacting for 70min, washing the glass for several times by using a large amount of deionized water and ethanol, drying the glass at 60 ℃ for 30min to form polypyrrole films, namely electrochromic layers, on the upper surface and the lower surface of the conductive glass, wiping the polypyrrole films on the upper surface of the conductive glass by using a cotton swab dipped with N, N-dimethylformamide, and finishing the growth of the electrochromic layers; as shown in fig. 3a, the polypyrrole film is in a continuous film form with accumulated particles, and can be uniformly distributed on the surface of the transparent substrate, so that the negative electrode current collector has good conductivity;
the specific preparation process of the polypyrrole polymerization growth solution comprises the following steps: firstly, measuring 90mL of deionized water, sequentially adding 10mL of methanol and 3.244g of ferric chloride hexahydrate, and marking as a solution A; then, 45mL of deionized water is measured, 5mL of methanol and 0.8mL of pyrrole monomer are sequentially added, and the solution is marked as solution B; cooling the solution A and the solution B to 4-8 ℃, and then pouring the solution A and the solution B into a 250mL beaker together for mixing to obtain a polypyrrole polymeric growth solution;
step3 depositing a conductive metal layer: selecting Ag as the conductive metal, transferring the glass with the polypyrrole film obtained in Step2 into an evaporation machine, and enabling one side of the glass with the polypyrrole film to face an Ag evaporation source; in the evaporation process, the distance between the polypyrrole film and the Ag evaporation source is fixed to be 50cm, the polypyrrole film is kept rotating at the speed of 20r/min, and the pressure in the working chamber of the evaporation machine is kept to be 2.4 multiplied by 10-4Pa or less, the evaporation rate being maintained at
Finally, plating a silver film, namely a conductive metal layer, on the lower surface of the electrochromic layer to finish the preparation of the negative current collector; the lower surface of the negative current collector is a mirror surface, and the upper surface of the negative current collector presents a dark brown appearance; as shown in fig. 3b, the obtained silver thin film can be observed to have a two-dimensional continuous film form under a low-power scanning electron microscope image, and can provide two-dimensional conductivity for the negative electrode current collector; as shown in fig. 3c, the high power scanning electron microscope image shows that the silver thin film prepared by the method has a porous structure with uniform pores, and the porous structure is used as a transmission passage for ions to permeate the silver thin film and reach the polypyrrole thin film, thereby being beneficial to realizing the electrochromic function;
4) assembling the super capacitor:
firstly, respectively mixing and stirring 85 wt% of anode energy storage electrode material and cathode energy storage electrode material, 10 wt% of acetylene black and 5 wt% of 1-methyl-2-pyrrolidone (NMP) solvent for 6 hours to form anode energy storage electrode slurry and cathode energy storage electrode slurry; then respectively coating the anode energy storage electrode slurry and the cathode energy storage electrode slurry on the upper surface of an anode current collector and the lower surface of a cathode current collector (the lower surface of a silver film) in a scraping manner, and drying at 80 ℃ for 12h to form an anode energy storage electrode layer and a cathode energy storage electrode layer; wherein, the positive current collector adopts commercially available ITO/Glass conductive Glass; the loading amounts of the anode energy storage electrode layer and the cathode energy storage electrode layer are respectively 2.8 and 3.3mg/cm2(ii) a The positive energy storage electrode layer and the positive current collector form a positive electrode of the super capacitor, the negative energy storage electrode layer and the negative current collector form a negative electrode of the super capacitor, then the hollow PDMS frame is clamped between the positive electrode and the negative electrode of the super capacitor to be used as a diaphragm, and LiClO with the concentration of 1mol/L is injected by an injector4Injecting the aqueous solution into the PDMS frame clip as an electrolyte; and finally, sealing the whole super capacitor by adopting waterproof silica gel to finish the assembly of the super capacitor.
When the transparent substrate of the negative current collector is a flexible ethylene terephthalate (PET) film with the thickness of 50 μm, and correspondingly the positive current collector is an ITO/PET flexible conductive filmThe spacing distance between the positive electrode and the negative electrode of the film and the super capacitor is 50 mu m, and the loading amounts of the positive energy storage electrode layer and the negative energy storage electrode layer are 1.0 and 1.2mg/cm respectively2。
And (3) testing the performance of the super capacitor:
fig. 4a is an electrochemical in situ visible light reflectance spectrum test result of a negative current collector; when the potential applied on the negative current collector is increased from 0V to-0.9V, the reflectivity of the negative current collector to visible light with the wavelength of more than 480nm is remarkably increased, and the result shows that the negative current collector can realize an electrochromic function by adjusting the potential. FIG. 4b is a plot of charge density versus optical density for the negative current collector, showing that the negative current collector has a density as high as 111.7cm2The electrochromic efficiency (optical density/charge density) of the/C is obviously higher than that of most of the existing electrochromic thin film materials. Fig. 4c shows the change of the reflectivity of the negative electrode current collector to visible light with a wavelength of 650nm during the potential change, wherein 0.56s is required for the transition from the low-reflectivity state to the high-reflectivity state, and only 0.52s is required for the transition from the high-reflectivity state to the low-reflectivity state. Fig. 4d is a graph of a relationship between the number of cycles of discoloration of the negative current collector and the retention rate of reflectance conversion, and when the number of cycles of discoloration reaches 1000 times, the retention rate of reflectance change of the negative current collector is still maintained at about 95%, which proves that the negative current collector obtained in this embodiment has good electrochromic cycle stability.
FIG. 5a is a graph of cyclic voltammetry test results for a supercapacitor demonstrating a good electrochemical energy storage process of the supercapacitor type, with device voltages up to 1.8V. FIG. 5b shows the result of the measurement of the charging and discharging time of the super capacitor under different charging and discharging current densities, after calculation, the area specific capacitance of the super capacitor is 1mA/cm2The highest current density can reach 241.1mF/cm2Corresponding to an energy density of 112.2. mu. Wh/cm2The result is obviously superior to the existing transparent electrochromic super capacitor, and simultaneously shows that the super capacitor obtained by the embodiment has the characteristic of high energy density. FIG. 5c is a schematic view of a super capacitorAccording to an optical response curve in the charging process, the reflectivity of the negative current collector is remarkably increased along with the increase of the voltage in the charging process, and then the reflectivity of the negative current collector is correspondingly reduced along with the reduction of the voltage in the discharging process, so that the inner energy of the super capacitor is well visualized through electrochromism. Fig. 5d is a color change graph of the super capacitor in the charging and discharging processes, where L denotes color brightness and b denotes chromaticity, which proves that the super capacitor obtained in this embodiment has obvious visual color change, and is convenient for the user to observe.
Fig. 6(a) is a cyclic voltammetry test result graph of a flexible supercapacitor made by respectively using an ITO/PET flexible conductive film and a PET flexible film as a positive current collector and a transparent substrate at different bending angles, and the result shows that the flexible supercapacitor can maintain stable energy storage performance at different bending angles; fig. 6(b) is the color change of the flexible supercapacitor under a black background, and a significant electrochromic color change can be observed under the black background, so that the electrochromic of the supercapacitor of the present application is not affected by the environmental color and is non-transparent.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. A super capacitor with electrochromic function and high energy density is characterized in that the super capacitor comprises a negative current collector, a negative energy storage electrode layer, an electrolyte, a positive energy storage electrode layer and a positive current collector from top to bottom in sequence;
the negative current collector comprises a transparent substrate, an electrochromic layer and a conductive metal layer from top to bottom; the transparent substrate allows part or all of visible light to penetrate through; the electrochromic layer can realize different color changes under electrochemical stimulation; the conductive metal layer can reflect part or all visible light and has a porous structure penetrating through the upper surface and the lower surface, and ions in the electrolyte can penetrate through the porous structure of the conductive metal layer to be in contact with the electrochromic layer in the charge and discharge processes of the super capacitor, so that the negative current collector has a reflection-type electrochromic function.
2. The supercapacitor having both electrochromic function and high energy density according to claim 1, wherein the lower surface of the electrochromic layer has a surface roughness, and the conductive metal is deposited on the lower surface of the electrochromic layer by physical vapor deposition to form a conductive metal layer.
3. The supercapacitor with electrochromic function and high energy density according to claim 1, wherein the transparent substrate is made of common glass, conductive glass or a PET flexible film, and the thickness of the transparent substrate is 30-10000 μm.
4. The supercapacitor with both electrochromic function and high energy density according to claim 1, wherein the electrochromic layer is made of polypyrrole and is grown on the lower surface of the transparent substrate by using a chemical polymerization method; the thickness of the electrochromic layer is 50-1000 nm.
5. The supercapacitor with the electrochromic function and the high energy density according to claim 1, wherein the conductive metal layer is made of silver, aluminum, copper or gold, and the thickness of the conductive metal layer is 50-6000 nm.
6. The supercapacitor with both electrochromic function and high energy density according to claim 1, wherein the negative energy storage electrode layer uses a molybdenum oxide nanobelt as a main material, and carbon nanotubes are mixed in the molybdenum oxide nanobelt, so that the negative energy storage electrode layer has a large number of pores.
7. The supercapacitor with both electrochromic function and high energy density according to claim 1, wherein the positive energy storage electrode layer is made of manganese dioxide nanoparticles.
8. The supercapacitor with both electrochromic function and high energy density according to claim 1, wherein the positive electrode current collector is made of aluminum foil, titanium foil, carbon material thin film, ITO/Glass conductive Glass or ITO/PET flexible conductive film.
9. A preparation method of a super capacitor with electrochromic function and high energy density is characterized by comprising the following steps:
1) preparing a negative energy storage electrode material:
adding 1g of molybdenum metal powder into 5mL of deionized water to form uniformly dispersed suspension; then, slowly adding 20mL of hydrogen peroxide solution with the mass fraction of 30% into the suspension, and continuously stirring for 30min to obtain a suspension after reaction; transferring the suspension after the reaction into a stainless steel autoclave with polytetrafluoroethylene as an inner liner, and heating to 220 ℃ for 72 hours to obtain white precipitate; washing the white precipitate for several times by using deionized water to obtain molybdenum oxide powder; finally, vacuum drying the molybdenum oxide powder at 60 ℃ for 8h to obtain a molybdenum oxide nanobelt; mixing the molybdenum oxide nanobelt and the carbon nanotube according to the mass ratio of 9:1, and uniformly mixing by mechanical grinding to obtain a negative energy storage electrode material;
2) preparing a positive energy storage electrode material:
dissolving 0.3g of potassium permanganate in 30mL of deionized water, and continuously stirring for 30min at room temperature until the potassium permanganate is completely dissolved; adding 0.05g of glucose into the solution to reduce potassium permanganate, and stirring for 12 hours; then, centrifugally cleaning for 3 times by using deionized water, and drying for 6 hours at 60 ℃ to obtain manganese dioxide nanoparticles;
3) preparing a negative current collector:
cleaning of Step1 transparent substrate: preparing a transparent substrate by using common glass, placing the glass with the thickness of 2mm in deionized water for ultrasonic cleaning for 20min, then transferring the glass into absolute ethyl alcohol for ultrasonic cleaning for 20min, and finally placing the glass in a blast drying oven at 60 ℃ for drying for later use;
step2 growth of electrochromic layer: 150mL of polypyrrole polymerization growth solution is filled in a reaction container, the cleaned and dried glass is placed in the polypyrrole polymerization growth solution, the glass is placed perpendicular to the bottom of a beaker and is completely immersed in the polypyrrole polymerization growth solution, the glass is taken out of the polypyrrole polymerization growth solution after reaction for 70min, a large amount of deionized water and ethanol are used for washing for a plurality of times, drying is carried out for 30min at 60 ℃, polypyrrole films, namely electrochromic layers, are formed on the upper surface and the lower surface of the conductive glass, and then the polypyrrole films on the upper surface of the conductive glass are wiped off by using a cotton swab dipped with N, N-dimethylformamide, so that the growth of the electrochromic layers is completed;
step3 depositing a conductive metal layer: selecting Ag as the conductive metal, transferring the glass with the polypyrrole film obtained in Step2 into an evaporation machine, and enabling one side of the glass with the polypyrrole film to face an Ag evaporation source; in the evaporation process, the distance between the polypyrrole film and the Ag evaporation source is fixed to be 50cm, the polypyrrole film is kept rotating at the speed of 20r/min, and the pressure in the working chamber of the evaporation machine is kept to be 2.4 multiplied by 10-4Pa or less, the evaporation rate being maintained at
Finally, plating a silver film, namely a conductive metal layer, on the lower surface of the electrochromic layer to finish the preparation of the negative current collector;
4) assembling the super capacitor:
firstly, respectively mixing and stirring 85 wt% of anode energy storage electrode material and cathode energy storage electrode material, 10 wt% of acetylene black and 5 wt% of 1-methyl-2-pyrrolidone solvent for 6 hours to form anode energy storage electrode slurry and cathode energy storage electrode slurry; respectively coating the anode energy storage electrode slurry and the cathode energy storage electrode slurry on the upper surface of an anode current collector and the lower surface of a cathode current collector by scraping, and drying at 80 ℃ for 12h to form an anode energy storage electrode layer and a cathode energy storage electrode layer; the positive current collector adopts ITO/Glass conductive Glass; the positive energy storage electrode layer and the positive current collector form a positive electrode of the super capacitor, the negative energy storage electrode layer and the negative current collector form a negative electrode of the super capacitor, then the hollow PDMS frame is placed between the positive electrode and the negative electrode of the super capacitor to be used as a diaphragm, and LiClO with the concentration of 1mol/L is injected by using an injector4Injecting aqueous solution into PDMS frame clip as electricityDecomposing the materials; and finally, sealing the whole super capacitor by adopting waterproof silica gel to finish the assembly of the super capacitor.
10. The preparation method of the supercapacitor with the electrochromic function and the high energy density according to claim 1, wherein the specific preparation process of the polypyrrole polymerization growth solution is as follows: firstly, measuring 90mL of deionized water, sequentially adding 10mL of methanol and 3.244g of ferric chloride hexahydrate, and marking as a solution A; then, 45mL of deionized water is measured, 5mL of methanol and 0.8mL of pyrrole monomer are sequentially added, and the solution is marked as solution B; and cooling the solution A and the solution B to 4-8 ℃, and then pouring the solution A and the solution B into a beaker together for mixing to obtain the polypyrrole polymeric growth solution.
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| CN117878369A (en) * | 2023-11-29 | 2024-04-12 | 东华大学 | Flexible color-changing battery with multiple colors capable of being reversibly changed and preparation method thereof |
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| CN117878369A (en) * | 2023-11-29 | 2024-04-12 | 东华大学 | Flexible color-changing battery with multiple colors capable of being reversibly changed and preparation method thereof |
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