CN112448069A - Metal-air battery and super capacitor integrated device and preparation method thereof - Google Patents

Metal-air battery and super capacitor integrated device and preparation method thereof Download PDF

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Publication number
CN112448069A
CN112448069A CN202011285973.6A CN202011285973A CN112448069A CN 112448069 A CN112448069 A CN 112448069A CN 202011285973 A CN202011285973 A CN 202011285973A CN 112448069 A CN112448069 A CN 112448069A
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China
Prior art keywords
metal
air battery
electrode
super capacitor
electrolyte
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CN202011285973.6A
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Inventor
孟垂舟
候占瑞
王鹏
李国显
郭士杰
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Hebei University of Technology
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Hebei University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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

Abstract

The invention provides a metal-air battery and super capacitor integrated device and a preparation method thereof, wherein the metal-air battery and super capacitor integrated device comprises a metal-air battery part, a super capacitor part and an isolating layer, wherein the metal-air battery and the super capacitor are respectively positioned on two sides of the isolating layer, the metal-air battery and the super capacitor are positioned in the same plane and arranged in parallel, and the metal-air battery and the super capacitor share the same anode and cathode to form an integrated energy device. The positive pole and the negative pole of the integral device are respectively provided with a lead which is connected with external equipment, and the surface of the device is provided with a packaging film. The metal-air battery and super capacitor integrated device has the advantages of high energy density of a metal-air battery and high power density of a super capacitor, improves the overall energy utilization efficiency, shows excellent flexibility, and is suitable for the fields of flexible wearable equipment, health care robots and the like.

Description

Metal-air battery and super capacitor integrated device and preparation method thereof
Technical Field
The invention belongs to the field of flexible energy devices, and particularly relates to a metal-air battery and supercapacitor integrated device and a preparation method thereof.
Background
The integrated hybrid energy device combines the advantages of the metal-air battery and the super capacitor, and avoids the defects of the metal-air battery and the super capacitor to a great extent, so that the integrated hybrid energy device has the characteristics of high specific power density and specific energy density, stable output and cycle performance, economy, environmental protection, long service life and the like. The integrated hybrid energy device has a simple structure, can be prepared into a planar film form, and can be flexible. Therefore, the integrated hybrid energy device has wide application prospect in the fields of wearable electronic equipment, small and miniature consumer electronic equipment and the like. The primary function of the device is to provide a stable power system as a flexible electronic device.
The traditional combination mode of the metal-air battery and the super capacitor is a series-parallel connection mode through an external circuit, and the mode has the defects that the output performance is hindered by large connection internal resistance, and the device is not easy to be flexible. In summary, a new design method is needed to reduce or even avoid the connection internal resistance of the combined device of the metal-air battery and the super capacitor and to achieve the performance of flexibility and the like.
Disclosure of Invention
In view of this, the present invention is directed to a metal-air battery and supercapacitor integrated device and a method for manufacturing the same, which solve the problems of low working voltage, low capacity, low energy conversion rate of the device, poor flexibility and poor safety.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the utility model provides a metal-air battery and ultracapacitor system integration device which characterized in that: the metal air battery and the super capacitor are respectively positioned on two sides of the partition layer, the metal air battery and the super capacitor are arranged in the same plane and are arranged in parallel, the metal air battery is composed of a positive electrode in contact with air and a negative electrode with a metal electrode, which are mixed with a layer of electrolyte, the super capacitor is composed of a positive electrode and a negative electrode, which are mixed with a layer of electrolyte, and the metal air battery and the super capacitor share the same positive electrode and the same negative electrode to form an integrated device integrated energy device. The positive pole and the negative pole of the integral device are provided with two leads which are connected with external equipment, and the surface of the device is provided with a packaging film.
The metal-air battery comprises one of a lithium-air battery, a zinc-air battery, a magnesium-air battery and an aluminum-air battery.
The super capacitor comprises one of an electric double layer super capacitor, a pseudo-capacitor super capacitor and a lithium ion capacitor.
The positive electrode and the negative electrode are composite material films with the characteristic of flexibility, and are one of electrode active substances loaded on a flexible carbon substrate or coated on a conductive current collector.
The electrolyte is one of liquid electrolytes such as acid, alkali, salt and ionic liquid or solid electrolytes developed based on the electrolyte, and is prepared by mixing a first solvent, a second solvent and a high polymer material, wherein the mass ratio of the first solvent to the second solvent to the high polymer material is (30-50): (10-20): (3-9), the first solvent in the electrolyte is deionized water or high-purity water, the second solvent in the electrolyte is an alkaline solution, the alkaline substance is one of sodium hydroxide and potassium hydroxide, and the high polymer material is preferably one of polypropylene glycol, polyacrylic acid or cellulose. In order to prevent the evaporation of water, a water retention agent can be added to enhance the water retention performance of the electrolyte, and the water retention agent comprises glycerol, tetraethylammonium hydroxide and the like.
The packaging film is a polymer film, preferably one of polyethylene terephthalate (PET), polyvinyl chloride (PU) or Polyimide (PI) films.
The lead is made of one of copper, silver, aluminum and gold and is in the shape of one of metal wires, lines or strips, and meanwhile, the lead and the electrodes are connected and fixed by silver paste.
A preparation method of a metal-air battery and super capacitor integrated device comprises the following steps:
(1) preparation of the positive electrode: placing a carbon cloth into a deposition solution, wherein the deposition solution is formed by mixing 100ml-130ml of ethylene glycol, 150ml-195ml of deionized water and 10g-13g of cobalt nitrate hexahydrate, depositing an active substance on the surface of the carbon cloth by adopting an electrodeposition method, the carbon cloth is a working electrode, a platinum sheet electrode is a counter electrode, a saturated calomel electrode is a reference electrode, carrying out electrochemical deposition under the condition that the constant potential is-0.9V-1.1V, the deposition time is 20-60min, drying the obtained carbon cloth for 2-2.6h at 60-78 ℃ in a nitrogen atmosphere in a tubular furnace, then reacting for 1-1.3h at 400-480 ℃ in an air atmosphere, and taking out the carbon cloth after the room temperature of the equipment is recovered to obtain an anode.
(2) Preparation of electrolyte layer: mixing a first solvent with a high molecular material, heating and stirring for 1-2 hours at 80-100 ℃, adding a second solvent when the high molecular material is completely dissolved, continuing heating and stirring until the solution is clear, cooling completely, pouring into a mold, and freezing and crosslinking for 6-15 hours at-30 to-50 ℃ to obtain the electrolyte layer.
(3) Preparing a cathode of the super capacitor: the active material, absolute ethanol, and binder were ultrasonically mixed and then coated onto a carbon cloth.
(4) Preparation of a zinc electrode: the zinc foil is selected as a zinc electrode, and the area of the zinc electrode is 1/3-1/2 of the common electrode.
(5) Integration: the negative electrode is tiled at the bottom, and the positive electrode is positioned at the top layer; coating silver paste on the contact surface of the metal electrode and the negative electrode for connection; the metal electrode and the positive electrode are connected by using a solid gel electrolyte; the partition layer is formed by attaching a transparent adhesive tape between the two electrodes so as to prevent the short circuit between the battery and the capacitor; the other part of the lower surface of the anode is connected with the other part of the upper surface of the cathode by adopting solid gel electrolyte.
(6) Leading wires: and respectively attaching one end of each of two stainless steel mesh strips dipped with conductive silver paste to the surface of the anode and the surface of the cathode of the integrated energy device, and placing the integrated energy device at room temperature for solidification.
(7) Packaging: and coating a layer of polymer film outside the device for thermoplastic packaging, and reserving vent holes on the surface of the metal-air battery.
The thickness of the zinc foil in the step (4) is 0.05-0.3 mm.
The metal air battery and the public positive electrode and the public negative electrode of the super capacitor in the integrated energy device are subjected to oxidation reaction to generate metal ions during discharging, and the metal ions and hydroxyl ions (OH-) in the strong alkaline electrolyte are combined into tetrahydroxy metal ions. If the alkalinity is insufficient or the tetrahydroxy metal ions are saturated, the hydroxide ions will undergo dehydration to produce zinc oxide. Meanwhile, the common anode takes oxygen as an active substance, electrons are formed under the action of a catalyst and combined with moisture in the electrolyte to form hydroxide ions, and the electrons pass through the common cathode and are transmitted to the common anode through the electrolyte to form current, namely, the current is discharged through the super capacitor, so that the discharge action is generated. Due to the concentration effect and the relation of balanced charges, hydroxide ions in the solid gel electrolyte move to a negative electrode, and positive ions move to a positive electrode; during charging, firstly, a metal sheet electrode of the metal-air battery part is subjected to a reduction reaction, and tetrahydroxy metal ions in alkaline electrolyte react to obtain electrons and simple substance zinc which is deposited on the surface of the electrode; there is also the phenomenon that zinc oxide dissolves in a strong alkaline environment and obtains electrons to form elemental zinc. The positive electrode is subjected to oxidation reaction, hydroxyl in the electrolyte loses electrons, and the electrons enter the alkaline gel electrolyte from the positive electrode and are transmitted to the metal electrode, so that charging action is formed. Ions in the solid electrolyte are influenced by the electric field, anions move to the positive electrode, and cations move to the negative electrode.
Compared with the prior art, the metal-air battery and super capacitor integrated device and the preparation method thereof have the following advantages:
(1) the energy device provided by the invention has high energy utilization rate. Compared with the energy utilization rate of a metal-air battery monomer, the energy utilization rate is improved by nearly 15 percent, and the energy utilization rate is improved;
(2) the energy device realizes the integrated flexible integration without external circuit connection. The internal resistance of the whole device is greatly reduced due to no external circuit connection, the device shows excellent flexibility, and most wearable electronic devices can be perfectly compatible.
(3) The integrated energy device is characterized in that the metal-air battery and the super capacitor share the positive electrode and the negative electrode of the super capacitor to form a parallel structure, the metal-air battery is stored in the super capacitor after obtaining energy and then discharges, and the charging and discharging stability and rapidity are improved.
(4) The metal-air battery and the super capacitor are combined into an integrated flexible hybrid energy device, so that the problem that a large resistor is caused by external lead connection is avoided, the energy utilization rate is improved, the flexibility of the device is realized, and the film form of the device is more suitable for wearable electronic equipment.
Drawings
FIG. 1 is a metal-air battery and supercapacitor integrated device;
fig. 2 is a zinc-air cell energy device in comparative example 1;
FIG. 3 is an equivalent circuit diagram of the energy device of the present invention;
FIG. 4 is a data graph of energy utilization of the energy device of the present invention;
FIG. 5 shows the discharge of the integrated device at different discharge current densities;
FIG. 6 shows the metal-air cell and integrated device of example 1 and comparative example 1 at 2mA/cm2Performing lower cycle charge and discharge;
FIG. 7 shows the metal-air cell and integrated device of example 2 and comparative example 2 at 2mA/cm2Performing lower cycle charge and discharge;
FIG. 8 shows the results of the metal-air cell and the integrated device in example 3 and comparative example 3 at 2mA/cm2Performing lower cycle charge and discharge;
FIG. 9 shows open circuit potentials of zinc-air cells of comparative example 1 and example 4;
FIG. 10 is a plot of the cycling at 2mA/cm 2 current densities for comparative example 1 and example 4;
FIG. 11 is a discharge curve of comparative example 1 and example 4 at different discharge current densities;
FIG. 12 is a plot of discharge at 2mA/cm 2 discharge current density for comparative example 1 and example 4.
Description of the drawings:
1-a partition layer; 2-metal-air battery; 3-a supercapacitor; 4-positive electrode; 5-negative pole; 6-electrolyte; 7-a metal electrode; 8-lead.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
The embodiment provides an integrated hybrid energy device combining a zinc-air battery and an asymmetric supercapacitor, which is used for providing power for a wearable electronic device, and as shown in fig. 1, the energy device comprises a common electrode, an alkaline gel electrolyte, a zinc electrode, a supercapacitor counter electrode and a transparent adhesive tape from top to bottom, wherein the common electrode and the supercapacitor counter electrode are 5cm long, 2cm wide and 0.5mm thick; the length and width of the zinc electrode are both 2cm, and the thickness is 0.1 mm; gel 0.5 mm; the length of the transparent adhesive tape is 1cm, the width of the transparent adhesive tape is 2cm, and the thickness of the transparent adhesive tape is 0.5 mm; the overall thickness of the device is 1.5 mm.
The preparation method of the integrated hybrid energy device combining the zinc-air battery and the asymmetric supercapacitor in the embodiment comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing O at a ratio of 1:8, mixing the two in a beaker, placing a magnetic stirrer, and sealing the mouth of the beaker by a diaphragmPutting the mixture into a magnetic water bath, stirring the mixture at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the mixture until the colloid is faint yellow, taking the colloid out, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid into a refrigerator for freezing and crosslinking for 6-12 hours, repeating the steps for 3-4 times, and adding a water-retaining agent, wherein the water-retaining agent is a third solvent and comprises polyacrylic acid, tetraethylammonium hydroxide and the like, and the first solvent is specifically matched: a second solvent: a third solvent: the high molecular material is (15-25): (10-20): (10-20): (3-9).
3. Preparing a counter electrode of the super capacitor; mixing the activated carbon, the conductive graphite and the binder for the supercapacitor according to the ratio of 8:1:1, adding a proper amount of absolute ethyl alcohol, dispersing in water bath ultrasound for 30min to fully mix the slurry, and then uniformly coating the slurry on carbon cloth to obtain the counter electrode of the supercapacitor.
4. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
5. And (3) assembling an integrated device, assembling all parts according to the structure shown in the figure, attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the common electrode and the counter electrode of the super capacitor respectively, and cooling the silver paste.
6. And packaging the integrated device, namely coating the integrated device by using a PI film, and packaging by adopting a thermoplastic packaging mode, wherein holes are formed on the surface of the common electrode.
Example 2
The embodiment provides an integrated hybrid energy device combining a zinc-air battery and an asymmetric supercapacitor, which is used for providing power for a wearable electronic device, and comprises a common electrode, an alkaline gel electrolyte, a zinc electrode, a supercapacitor counter electrode and a transparent adhesive tape from top to bottom, wherein the common electrode and the supercapacitor counter electrode are 5cm long, 2cm wide and 0.5mm thick; the length and width of the zinc electrode are both 2cm, and the thickness is 0.1 mm; gel 0.5 mm; the length of the transparent adhesive tape is 1cm, the width of the transparent adhesive tape is 2cm, and the thickness of the transparent adhesive tape is 0.5 mm; the overall thickness of the device is 1.5 mm.
The preparation method of the integrated hybrid energy device combining the zinc-air battery and the asymmetric supercapacitor in the embodiment comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 30 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing the two according to the proportion of 1:8, mixing the two in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by a diaphragm, placing the beaker in a magnetic water bath, stirring the solution at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the solution until the colloid is faint yellow, taking out the mixture, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, repeating the steps for 3-4 times, and adding a water-retaining agent, namely a third solvent which comprises polyacrylic acid, tetraethylammonium hydroxide and the like, wherein the first solvent is specifically matched: a second solvent: a third solvent: the high molecular material is (15-25): (10-20): (10-20): (3-9).
3. Preparing a counter electrode of the super capacitor; mixing the activated carbon, the conductive graphite and the binder for the supercapacitor according to the ratio of 8:1:1, adding a proper amount of absolute ethyl alcohol, dispersing in water bath ultrasound for 30min to fully mix the slurry, and then uniformly coating the slurry on carbon cloth to obtain the counter electrode of the supercapacitor.
4. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
5. And (3) assembling the integrated device, assembling all parts according to the structure shown in figure 1, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the common electrode and the counter electrode of the supercapacitor, and cooling the silver paste.
6. And packaging the integrated device, namely coating the integrated device by using a PI film, and packaging by adopting a thermoplastic packaging mode, wherein holes are formed on the surface of the common electrode.
Example 3
The embodiment provides an integrated hybrid energy device combining a zinc-air battery and an asymmetric supercapacitor, which is used for providing power for a wearable electronic device, wherein a common electrode and a supercapacitor counter electrode are 5cm long, 2cm wide and 0.5mm thick; the length and width of the zinc electrode are both 2cm, and the thickness is 0.1 mm; gel 0.5 mm; the length of the transparent adhesive tape is 1cm, the width of the transparent adhesive tape is 2cm, and the thickness of the transparent adhesive tape is 0.5 mm; the overall thickness of the device is 1.5 mm.
The preparation method of the integrated hybrid energy device combining the zinc-air battery and the asymmetric supercapacitor in the embodiment comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing the two according to the proportion of 1:8, mixing the two in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by a diaphragm, placing the beaker in a magnetic water bath, stirring the solution at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 3g of KOH into the mixed solution, stirring the solution until the colloid is faint yellow, taking out the mixture, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, repeating the steps for 3-4 times, and adding a water-retaining agent, namely a third solvent which comprises polyacrylic acid, tetraethylammonium hydroxide and the like, wherein the first solvent is specifically matched: a second solvent: a third solvent: the high molecular material is (15-25): (10-20): (10-20): (3-9).
3. Preparing a counter electrode of the super capacitor; mixing the activated carbon, the conductive graphite and the binder for the supercapacitor according to the ratio of 8:1:1, adding a proper amount of absolute ethyl alcohol, dispersing in water bath ultrasound for 30min to fully mix the slurry, and then uniformly coating the slurry on carbon cloth to obtain the counter electrode of the supercapacitor.
4. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
5. And (3) assembling the integrated device, assembling all parts according to the structure shown in figure 1, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the common electrode and the counter electrode of the supercapacitor, and cooling the silver paste.
6. And packaging the integrated device, namely coating the integrated device by using a PI film, and packaging by adopting a thermoplastic packaging mode, wherein holes are formed in a packaging film on the surface of the common electrode.
Example 4
In this embodiment, as shown in fig. 2, the length and width of the air electrode, the electrolyte layer, and the zinc electrode are all 2cm, and the thicknesses of the air electrode, the electrolyte layer, and the zinc electrode are 0.5mm, and 0.1mm, respectively.
The preparation method of the zinc-air battery energy device comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to the following polyvinyl alcohol: deionized water: weighing tetraethyl ammonium hydroxide in a ratio of 1:4:4, mixing the tetraethyl ammonium hydroxide and the tetraethyl ammonium hydroxide in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by using a diaphragm, placing the beaker in a magnetic water bath, stirring the beaker at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the solution until the colloid is light yellow, taking the colloid out, pouring the colloid into a mold after cooling the colloid to eliminate internal bubbles, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, and repeating the steps for 3-4 times.
3. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
4. And (3) assembling the devices, namely assembling all parts according to the structure shown in fig. 2, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the air electrode and the zinc electrode, and cooling the silver paste.
5. And packaging the integrated device by using a PI film to coat the device and adopting a thermoplastic packaging mode, wherein the packaging film on the surface of the air electrode is provided with holes.
Example 4
The comparative example provides a zinc-air battery energy device, as shown in fig. 2, the length and width of the air electrode, the electrolyte layer and the zinc electrode are all 2cm, and the thicknesses of the air electrode, the electrolyte layer and the zinc electrode are 0.5mm, 0.5mm and 0.1mm respectively.
The preparation method of the energy device of the zinc-air battery in the comparative example comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to the following polyvinyl alcohol: deionized water: weighing tetraethyl ammonium hydroxide in a ratio of 1:4:4, mixing the tetraethyl ammonium hydroxide and the tetraethyl ammonium hydroxide in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by using a diaphragm, placing the beaker in a magnetic water bath, stirring the beaker at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the solution until the colloid is light yellow, taking the colloid out, pouring the colloid into a mold after cooling the colloid to eliminate internal bubbles, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, and repeating the steps for 3-4 times.
3. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
4. And (3) assembling the devices, namely assembling all parts according to the structure shown in fig. 2, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the air electrode and the zinc electrode, and cooling the silver paste.
5. And packaging the integrated device by using a PI film to coat the device and adopting a thermoplastic packaging mode, wherein the packaging film on the surface of the air electrode is provided with holes.
Comparative example 1
The comparative example provides a zinc-air battery energy device, as shown in fig. 2, the length and width of the air electrode, the electrolyte layer and the zinc electrode are all 2cm, and the thicknesses of the air electrode, the electrolyte layer and the zinc electrode are 0.5mm, 0.5mm and 0.1mm respectively.
The preparation method of the energy device of the zinc-air battery in the comparative example comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing the mixture and the water in a ratio of 1:8, mixing the mixture and the water in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by using a diaphragm, placing the beaker in a magnetic water bath, stirring the beaker at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the solution until the colloid is light yellow, taking the colloid out, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, and repeating the steps for 3-4 times.
3. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
4. And (3) assembling the devices, namely assembling all parts according to the structure shown in fig. 2, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the air electrode and the zinc electrode, and cooling the silver paste.
5. And packaging the integrated device by using a PI film to coat the device and adopting a thermoplastic packaging mode, wherein holes are formed on the surface of the air electrode.
Comparative example 2
This comparative example provides a zinc-air battery energy device, which comprises, as shown in fig. 2, an air electrode, an electrolyte layer, and a zinc electrode from top to bottom, all of which have a length and width of 2cm, and the thicknesses of the air electrode, the electrolyte layer, and the zinc electrode are 0.5mm, and 0.1mm, respectively.
The preparation method of the energy device of the zinc-air battery in the comparative example comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 30 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing the mixture and the water in a ratio of 1:8, mixing the mixture and the water in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by using a diaphragm, placing the beaker in a magnetic water bath, stirring the beaker at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 5g of KOH into the mixed solution, stirring the solution until the colloid is light yellow, taking the colloid out, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, and repeating the steps for 3-4 times.
3. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
4. And (3) assembling the devices, namely assembling all parts according to the structure shown in fig. 2, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the air electrode and the zinc electrode, and cooling the silver paste.
5. And packaging the integrated device by using a PI film to coat the device and adopting a thermoplastic packaging mode, wherein holes are formed on the surface of the air electrode.
Comparative example 3
The comparative example provides a zinc-air battery energy device, which comprises an air electrode 1, an electrolyte layer 2 and a zinc electrode 3 from top to bottom, wherein the length and the width of the air electrode 1, the electrolyte layer 2 and the zinc electrode 3 are all 2cm, and the thicknesses of the air electrode, the electrolyte layer and the zinc electrode are respectively 0.5mm, 0.5mm and 0.1 mm.
The preparation method of the energy device of the zinc-air battery in the comparative example comprises the following steps:
1. and preparing a common electrode, namely putting a carbon cloth into a deposition solution formed by mixing 100ml of ethylene glycol, 150ml of deionized water and 10g of cobalt nitrate hexahydrate, carrying out electrodeposition at the voltage of-0.9V for 20 minutes, taking out, repeatedly washing with absolute ethyl alcohol and deionized water, drying for 2 hours at the temperature of 60 ℃ in a nitrogen atmosphere, finally annealing for 1 hour at the temperature of 400 ℃ in an air atmosphere, cooling to room temperature, and taking out.
2. Preparation of electrolyte, according to PVA: h2Weighing the mixture and the water in a ratio of 1:8, mixing the mixture and the water in a beaker, placing a magnetic stirrer, sealing the mouth of the beaker by using a diaphragm, placing the beaker in a magnetic water bath, stirring the beaker at 80-100 ℃ until the solution is clear, pouring 10ml of solution containing 3g of KOH into the mixed solution, stirring the solution until the colloid is light yellow, taking the colloid out, cooling the colloid to eliminate internal bubbles, pouring the colloid into a mold, placing the colloid in a refrigerator for freeze crosslinking for 6-12 hours, and repeating the steps for 3-4 times.
3. And (3) preparing the zinc electrode, namely cutting the zinc foil with the required area by using a metal cutting knife, and flattening the zinc foil by adopting a pressing device to obtain the zinc electrode.
4. And (3) assembling the devices, namely assembling all parts according to the structure shown in fig. 1, respectively attaching two stainless steel mesh strips dipped with conductive silver paste to the surfaces of the air electrode and the zinc electrode, and cooling the silver paste.
5. And packaging the integrated device by using a PI film to coat the device and adopting a thermoplastic packaging mode, wherein holes are formed on the surface of the air electrode.
To verify the electrochemical performance of the zinc-air battery and cobalt oxide asymmetric supercapacitor, the integrated devices of examples 1, 2 and 3 were first usedFixing the special electrode clamp, testing by using an electrochemical workstation to respectively obtain the cyclic charge-discharge curves shown in figures 6-8, and obtaining the properties of the integrated energy device, such as energy utilization rate, stability and the like, and receiving Co3O4Deposition time and concentration of alkaline species. From FIG. 5, the device recovered to 0.1mA/m2When the current density is higher than the threshold value, the discharge platform is not obviously reduced, and the surface integrated device has a stable discharge platform.
Compared with a zinc-air battery monomer, the performance of the integrated device in the aspects of specific power density, charge-discharge efficiency, energy utilization rate and the like is greatly improved; meanwhile, the integrated device is used for discharging through the super capacitor, so that the service life of the zinc-air battery is greatly prolonged; the deposition amount affects the magnitude of the charging and discharging voltage of the device, but the influence on the overall energy utilization rate of the device is very little; the change of the alkaline concentration has certain influence on the charge and discharge voltage value of the device, the concentration is reduced, and the energy utilization rate is reduced accordingly. In the preparation of the zinc-air battery monomer device, compared with the electrolyte of a comparative example, the water-retaining agent is added, and the performance comparison is carried out, the result shows that the electrolyte added with the water-retaining agent is similar to the traditional gel electrolyte in the performances of charging voltage, discharging stability and the like of the battery, but the effective period of the electrolyte is greatly enhanced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. The utility model provides a metal-air battery and ultracapacitor system integration device which characterized in that: the battery comprises a partition layer (1), a metal-air battery (2) and a super capacitor (3); the metal-air battery (2) and the super capacitor (3) are respectively positioned on two sides of the partition layer (1), and the metal-air battery (2) and the super capacitor (3) are arranged in parallel in the same plane; the metal-air battery (2) and the super capacitor (3) are respectively provided with an anode (4) and a cathode (5) above and below the metal-air battery (2) and the super capacitor (3), and the anode (4) and the cathode (5) are shared by the metal-air battery (2) and the super capacitor (3); the metal-air battery (2) comprises an anode (4), an electrolyte (6) and a metal electrode (7), wherein the anode (4) is connected with the electrolyte (6), the electrolyte (6) is connected with the metal electrode (7), and the metal electrode (7) is connected with a cathode (5); the super capacitor comprises a positive electrode (4), an electrolyte (6) and a negative electrode (5); the positive pole (4) and the negative pole (5) of device are equipped with a lead wire (8) respectively, and the device surface is equipped with the encapsulation membrane, and the air vent that air got into is left on metal-air battery (2) positive pole surface.
2. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the metal-air battery (2) comprises one of a lithium air battery, a zinc air battery, an aluminum air battery and a magnesium air battery.
3. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the super capacitor (3) comprises one of a double electric layer super capacitor, a pseudo-capacitor super capacitor and a lithium ion capacitor.
4. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the positive electrode (4) and the negative electrode (5) are made of rigid or flexible composite material films, and are films formed by loading electrode active substances on a flexible carbon substrate or coating the electrode active substances on a conductive current collector.
5. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the electrolyte (6) is liquid electrolyte such as acid, alkali, salt, ionic liquid and the like or solid electrolyte developed based on the electrolyte, the electrolyte (6) is solid ionic gel electrolyte and prepared by mixing a first solvent, a second solvent and a high polymer material, and the mass ratio of the three is (30-50): (10-20): (3-9), the first solvent in the electrolyte is one of deionized water or high-purity water, the second solvent in the electrolyte is an alkaline solution, the alkaline substance is one of sodium hydroxide and potassium hydroxide, the high polymer material is one of polypropylene alcohol, polyacrylic acid or cellulose, and a humectant, such as one of glycerol and tetraethylammonium hydroxide, is added.
6. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the packaging film is a polymer film, preferably one of polyethylene terephthalate, polyvinyl chloride or polyimide film.
7. The integrated device of the metal-air battery and the supercapacitor as claimed in claim 1, wherein: the lead (8) is made of one of copper, silver, aluminum and gold and is in the shape of one of metal wires, lines or strips, and meanwhile, the lead and the electrodes are connected and fixed through silver paste.
8. The preparation method of the metal-air battery and supercapacitor integrated device according to any one of claims 1 to 7, which comprises the following steps:
(1) preparation of the positive electrode: placing a carbon cloth into a deposition solution, wherein the deposition solution is formed by mixing 100ml-130ml of ethylene glycol, 150ml-195ml of deionized water and 10g-13g of cobalt nitrate hexahydrate, depositing an active substance on the surface of the carbon cloth by adopting an electrodeposition method, the carbon cloth is a working electrode, a platinum sheet electrode is a counter electrode, a saturated calomel electrode is a reference electrode, carrying out electrochemical deposition under the condition that the constant potential is-0.9V-1.1V, the deposition time is 20-60min, drying the obtained carbon cloth for 2-2.6h at 60-78 ℃ in a nitrogen atmosphere in a tubular furnace, then reacting for 1-1.3h at 400-480 ℃ in an air atmosphere, and taking out the carbon cloth after the room temperature of the equipment is recovered to obtain an anode;
(2) preparation of electrolyte layer: mixing a first solvent and a high molecular material, heating and stirring for 1-2 hours at 80-100 ℃, adding a second solvent when the high molecular material is completely dissolved, continuously heating and stirring until the solution is clear, cooling completely, pouring into a mold, and freezing and crosslinking for 6-15 hours at-30 to-50 ℃ to obtain an electrolyte layer;
(3) preparing a cathode of the super capacitor: ultrasonically mixing an active substance, absolute ethyl alcohol and a bonding agent, and then coating the mixture on a carbon cloth;
(4) preparation of a zinc electrode: selecting zinc foil as a zinc electrode, wherein the area of the zinc electrode is 1/3-1/2 of a common electrode;
(5) integration: the negative electrode (5) is tiled at the bottom, and the positive electrode (4) is positioned at the top layer; silver paste is coated on the contact surface of the metal electrode (7) and the negative electrode (5) for connection; the metal electrode (7) is connected with the positive electrode (4) by using a solid gel electrolyte (6); the partition layer (1) is a transparent adhesive tape which is attached between the two electrodes to prevent the short circuit of the battery and the two parts of the capacitor; the other part of the lower surface of the anode (4) is connected with the other part of the upper surface of the cathode (5) by adopting a solid gel electrolyte (6);
(6) leading wires: respectively attaching one end of each of two stainless steel mesh strips dipped with conductive silver paste to the surface of the anode and the surface of the cathode of the integrated energy device, and placing the integrated energy device at room temperature for solidification;
(7) packaging: and a layer of polymer film is coated outside the device for thermoplastic packaging, and a vent hole is required to be reserved on the surface of the metal-air battery (2).
9. The method for preparing the integrated device of the metal-air battery and the supercapacitor as claimed in claim 8, wherein the method comprises the following steps: the thickness of the zinc foil in the step (4) is 0.05-0.3 mm.
CN202011285973.6A 2020-11-17 2020-11-17 Metal-air battery and super capacitor integrated device and preparation method thereof Pending CN112448069A (en)

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Application publication date: 20210305