CN112216518A - Flexible zinc ion hybrid capacitor and preparation method and application thereof - Google Patents
Flexible zinc ion hybrid capacitor and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of electrochemical energy storage, and discloses a flexible zinc ion hybrid capacitor and a preparation method and application thereof. The anode of the flexible zinc ion hybrid capacitor adopts flexible self-supporting activated carbon fibers with electrochemical activity, wherein the activated carbon fibers are activated carbon fiber cloth or activated carbon fiber bundles subjected to secondary activation treatment, and the pore distribution of the surface of the activated carbon fibers is regulated and controlled through a secondary activation process to form a hierarchical pore structure, so that an ion transmission channel of the flexible zinc ion hybrid capacitor when the flexible zinc ion hybrid capacitor is used as an anode of the flexible zinc ion hybrid capacitor is influenced, and the flexible zinc ion hybrid capacitor has high electrochemical activity, flexibility and self-supporting performance; the method is characterized in that metal zinc is deposited on a fibrous or film-shaped flexible substrate by adopting an electrochemical deposition method, or a zinc wire is directly used as the negative electrode of the flexible zinc ion hybrid capacitor. The flexible zinc ion hybrid capacitor has good flexible deformability and excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of novel electrochemical energy storage, and particularly relates to a flexible zinc ion hybrid capacitor and a preparation method and application thereof.
Background
In recent years, with the development of portable and wearable electronic products (such as foldable notebook computers, mobile phones, wearable smart clothes, etc.), flexible supercapacitors capable of supplying energy to the above devices have become a research hotspot in the field of flexible energy storage. However, the low energy density of flexible supercapacitors is a key bottleneck limiting their practical application. In order to improve the energy density of the flexible supercapacitor, a plurality of research teams at home and abroad carry out research on the following aspects, including: (1) flexible electrodes with high electrochemical performance were investigated; (2) the asymmetric super capacitor is designed to improve the voltage window and energy density of a super capacitor system.
Nevertheless, the energy density of flexible supercapacitors is still not ideal due to the energy storage mechanism of the supercapacitors themselves. In recent two years, water-based multivalent zinc ion hybrid capacitors have been proposed (Energy Storage Materials,2018,13:96-102.) in which positive and negative electrodes are respectively composed of active substances having a capacitive behavior and a battery behavior. Specifically, an activated carbon material is used as a positive electrode, metal zinc is used as a negative electrode, zinc sulfate aqueous solution is used as electrolyte, and a capacitance behavior of ion adsorption and desorption and a battery behavior of zinc dissolution-deposition are respectively generated on the positive electrode and the negative electrode; the novel electrochemical energy storage system shows much higher energy density than the traditional super capacitor system, and has the advantages of quick charge and discharge, super long cycle life, high safety and the like, thereby being widely concerned.
However, flexible zinc ion hybrid capacitors that can supply energy to portable, wearable electronics have not been reported.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the primary object of the present invention is to provide a flexible zinc ion hybrid capacitor.
The invention also aims to provide a preparation method of the flexible zinc ion hybrid capacitor.
The invention further aims to provide application of the flexible zinc ion hybrid capacitor in portable and wearable electronic products (such as foldable notebook computers, mobile phones, wearable smart clothes and the like).
The purpose of the invention is realized by the following scheme:
a flexible zinc ion hybrid capacitor comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode adopts flexible self-supporting active carbon fibers with electrochemical activity; the negative electrode is a galvanized flexible substrate, or a zinc wire is directly used as the negative electrode of the flexible zinc ion hybrid capacitor.
The active carbon fiber is active carbon fiber cloth or active carbon fiber bundles; the activated carbon fiber is prepared by adopting a secondary activation process;
preferably, the secondary activation process refers to one of the following three activation processes: (1) firstly, a secondary activation process of water vapor activation and potassium hydroxide activation is carried out; (2) firstly, activating by potassium hydroxide and activating by zinc chloride for the second time; (3) firstly, the secondary activation process of water vapor activation and zinc chloride activation is carried out.
The secondary activation process of firstly carrying out water vapor activation and then carrying out potassium hydroxide activation specifically comprises the following steps:
(1.1) placing the unactivated carbon fiber in a tube furnace, raising the temperature to 600-900 ℃ under the protection of inert gas, then introducing mixed gas of inert gas and water vapor, and activating for 10-60min to obtain the primary activated carbon fiber;
(1.2) soaking the primarily activated carbon fiber in a potassium hydroxide aqueous solution for 2-24h, taking out and drying to obtain a product 1, then placing the product 1 in a 600-plus-900 ℃ tube furnace for activation for 0.5-2h under a nitrogen atmosphere, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the secondarily activated carbon fiber.
The volume fraction of the water vapor in the mixed gas of the inert gas and the water vapor in the step (1.1) is 0.001-0.05%, and the volume fraction of the water vapor is preferably 0.01%; the flow rate of the water vapor was 0.5 x 10-4-1.5*10-4L/min；
The amount of the potassium hydroxide aqueous solution in the step (1.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the potassium hydroxide in the product 1 is 1:1-1: 5.
The secondary activation process of firstly activating by potassium hydroxide and then activating by zinc chloride specifically comprises the following steps:
(2.1) placing the unactivated carbon fiber in a potassium hydroxide solution for soaking for 2-24h, taking out and drying to obtain a product 2, placing the product 2 in a tube furnace at the temperature of 600-900 ℃ under an inert atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the once-activated carbon fiber;
(2.2) soaking the primarily activated carbon fiber in a zinc chloride aqueous solution for 2-24h, taking out and drying to obtain a product 3, placing the product 3 in a tube furnace at the temperature of 600-900 ℃ under an inert atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the secondarily activated carbon fiber.
The dosage of the potassium hydroxide aqueous solution in the step (2.1) meets the requirement that the mass ratio of the unactivated carbon fiber to the potassium hydroxide in the product 2 is 1:1-1: 5;
the dosage of the zinc chloride aqueous solution in the step (2.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the zinc chloride in the product 3 is 1:1-1: 5.
The secondary activation process of firstly carrying out water vapor activation and then carrying out zinc chloride activation specifically comprises the following steps:
(3.1) placing the unactivated carbon fiber in a tube furnace, raising the temperature to 600-900 ℃ under the protection of inert gas, then introducing mixed gas of inert gas and water vapor, and activating for 10-60min to obtain the primary activated carbon fiber;
(3.2) soaking the primarily activated carbon fiber in a zinc chloride aqueous solution for 2-24h, taking out and drying to obtain a product 4, placing the product 4 in a tube furnace with the temperature of 600-900 ℃ under the nitrogen atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the secondarily activated carbon fiber.
The volume fraction of the water vapor in the mixed gas of the inert gas and the water vapor in the step (3.1) is 0.001-0.05%, and the volume fraction of the water vapor is preferably 0.01%; the flow rate of the water vapor was 0.5 x 10-4-1.5*10-4L/min；
The dosage of the zinc chloride aqueous solution in the step (3.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the zinc chloride in the product 4 is 1:1-1: 5.
The activated carbon fiber has a specific surface area of 500-2500m2Preferably 850 to 2500 m/g2/g。
The zinc-plated flexible substrate is obtained by electrodepositing zinc on a fibrous or film-shaped flexible substrate by using a cyclic voltammetry through a two-electrode device, and specifically comprises the following steps: using a fibrous or film-shaped flexible substrate as a working electrode, a zinc foil as a counter electrode and a reference electrode, and 0.1-3mol/L ZnSO as electrolyte4In the water solution, the electrodeposition voltage interval is 2-3V, the sweep rate is 2-200mV/s, and after cyclic voltammetry is scanned for 10-200 circles, the water is used for washing, and then the drying is carried out, thus obtaining the galvanized flexible substrate negative electrode material;
the flexible substrate is a substrate formed by at least one of carbon fiber, carbon nanofiber, carbon nanotube, graphene and graphite alkyne material;
the electrolyte is a gel electrolyte system containing zinc salt, wherein the zinc salt is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc trifluoromethanesulfonate and bis (trifluoromethylsulfonyl) imide zinc.
The preparation method of the flexible zinc ion hybrid capacitor comprises the following steps:
(1) preparing a zinc salt into 0.1-3mol/L aqueous solution, adding the aqueous solution containing a monomer, a cross-linking agent and an initiator under the stirring condition for crosslinking for 10-30min, or adding the aqueous solution containing gel in a swelling state under the stirring condition to form uncured electrolyte glue;
(2) and assembling the flexible zinc ion hybrid capacitor according to the sequence of the cathode, the uncured gel electrolyte glue containing the zinc salt and the anode, and obtaining the flexible zinc ion hybrid capacitor after the gel electrolyte is completely polymerized.
The monomer in the step (1) is preferably acrylamide, the cross-linking agent is preferably N, N' -methylene-bisacrylamide, and the initiator is preferably ammonium persulfate.
According to the invention, an activated carbon fiber bundle or activated carbon fiber cloth with a hierarchical pore structure after secondary activation process treatment is used as a flexible self-supporting anode with electrochemical activity, metal zinc is deposited on a fibrous or film-shaped flexible substrate, or zinc wires are directly used as a cathode, and a gel electrolyte containing zinc ions is used, so that a flexible zinc ion hybrid capacitor with excellent electrochemical performance is designed, and the practical application of the flexible zinc ion hybrid capacitor in the fields of flexible energy storage and portable and wearable electronic products is promoted.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the active carbon fiber cloth or the active carbon fiber bundle is used as the anode of the flexible zinc ion hybrid capacitor, the high specific surface area and the developed hierarchical pore structure of the active carbon fiber cloth or the active carbon fiber bundle are favorable for obtaining high specific capacity, so that the electrochemical performance of the constructed flexible zinc ion hybrid capacitor is remarkably improved, and the energy storage requirement of a flexible wearable electronic product is favorably met.
2. The flexible positive electrode of the active carbon fiber is a self-supporting material, a current collector and an additional coating process are not needed, the zinc negative electrode is rich in raw materials and low in cost, and the flexible positive electrode is suitable for large-scale production and practical application.
Drawings
FIG. 1 is N of carbon fiber and secondarily activated carbon fiber in example 12Adsorption and desorption curve chart.
FIG. 2 is a scanning electron micrograph of a secondary activated carbon fiber in example 1.
FIG. 3 is a constant current charge and discharge curve at a current density of 2A/g for the flexible zinc ion hybrid capacitor based on a secondary activated carbon fiber anode in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Flexible zinc ion hybrid capacitor based on active carbon fiber (water vapor-potassium hydroxide secondary activation process) anode and galvanized carbon fiber cathode
Preparation of active carbon fiber anode
(1) Placing 0.5g of unactivated commercial carbon fiber sample in a tube furnace, heating to 800 ℃ at a speed of 20 ℃/min under the protection of argon atmosphere, introducing a mixed gas of argon and water vapor (the volume fraction of the water vapor is 0.01%) into the tube furnace for activation for 30min, wherein the flow rate of the water vapor is 1 x 10-4L/min. Reducing the temperature to room temperature under the protection of argon to prepare the active carbon fiber (ACF1) which is activated by water vapor for one time for standby;
(2) 0.1g of ACF1 is soaked in 5mol/L potassium hydroxide solution for 24 hours;
(3) and (3) fully drying the soaked ACF1 in a forced air oven at the temperature of 60 ℃, wherein the mass ratio of ACF1 to potassium hydroxide in the dried product is 1: 4;
(4) in nitrogen atmosphere, activating the ACF1 in the step (3) in a tube furnace at 850 ℃ for 1h, heating up at the speed of 5 ℃/min, cooling, repeatedly washing with deionized water until the washed solution is neutral, and drying to obtain the secondary activated carbon fiber (ACF2), wherein the specific surface area is 2100m2/g(N2The absorption and desorption curve is shown in figure 1), the scanning electron microscope image is shown in figure 2, and the scanning electron microscope image is used as the positive electrode of the flexible zinc ion hybrid capacitor;
preparation of (II) galvanized carbon fiber flexible negative electrode
(1) The carbon fibers were soaked in acetone to remove the surface polymer coating, then washed several times with deionized water and ethanol and dried. Adopting a two-electrode device to electrodeposit zinc on the surface of carbon fiber by cyclic voltammetry, specifically taking the carbon fiber as a working electrode, zinc foil as a counter electrode and a reference electrode, and 2mol/L ZnSO as electrolyte4The electrodeposition voltage of the aqueous solution is 2-3V, the sweep rate is 50mV/s, the cyclic voltammetry scans for 100 circles, the aqueous solution is washed with deionized water for three times, and the aqueous solution is dried for 24 hours at room temperature under the vacuum condition, namelyObtaining a galvanized carbon fiber flexible negative electrode;
(III) preparation of gel electrolyte
(1) 23g of ZnSO4·7H2Adding O into 40ml of deionized water, and stirring to dissolve;
(2) adding 4g of acrylamide into the solution under strong magnetic stirring at 40 ℃;
(3) adding 2mg of N, N' -methylene-bisacrylamide serving as a cross-linking agent and 50mg of ammonium persulfate serving as an initiator into the solution at 40 ℃ under strong magnetic stirring for 0.5 hour to form uncured electrolyte glue;
(IV) preparation of flexible zinc ion hybrid capacitor
And assembling the flexible zinc ion hybrid capacitor according to the sequence of the flexible cathode of the galvanized carbon fiber, the uncured electrolyte glue containing zinc salt and the anode of the activated carbon fiber, and keeping the device at 70 ℃ for 2 hours to ensure that the gel electrolyte is completely polymerized to obtain the flexible zinc ion hybrid capacitor. The constant current charge and discharge curve of the flexible zinc ion hybrid capacitor is shown in fig. 3. Based on the calculation of the quality of the anode material, the maximum specific capacity of the flexible zinc ion hybrid capacitor is 142 mAh/g.
Example 2
Flexible zinc ion hybrid capacitor based on active carbon fiber (potassium hydroxide-zinc chloride secondary activation process) anode and galvanized carbon fiber cathode
Preparation of active carbon fiber anode
(1) 0.1g of unactivated commercial carbon fiber sample is placed in 5mol/L potassium hydroxide solution for soaking for 24 hours, then the sample is placed in a forced air oven for full drying at the temperature of 60 ℃, and the mass ratio of the unactivated carbon fiber to the potassium hydroxide in the dried product is 1: 3;
(2) activating the carbon fiber in the step (1) in a tube furnace at 850 ℃ for 1h in nitrogen atmosphere, wherein the heating rate is 5 ℃/min, repeatedly washing the carbon fiber by deionized water after cooling until the washed solution is neutral, and drying to obtain the activated carbon fiber (ACF1) which is activated by potassium hydroxide for one time for later use;
(3) and (3) soaking the ACF1 in the step (2) in 5mol/L zinc chloride solution for 24 hours, and then putting the solution into a blast oven to be fully dried at the temperature of 60 ℃, wherein the mass ratio of the ACF1 to the zinc chloride in the dried product is 1: 4.5, placing the dried product in a tube furnace at 850 ℃ for activation for 0.5h under the inert atmosphere, wherein the heating rate is 5 ℃/min, repeatedly washing the product by using deionized water after cooling until the washed solution is neutral, and drying the product to obtain secondarily activated carbon fibers (ACF2) which are used as the positive electrode of the flexible zinc ion mixed capacitor;
preparation of (II) galvanized carbon fiber flexible negative electrode
(1) The carbon fibers were soaked in acetone to remove the surface polymer coating, then washed several times with deionized water and ethanol and dried. Adopting a two-electrode device to electrodeposit zinc on the surface of carbon fiber by cyclic voltammetry, specifically taking the carbon fiber as a working electrode, zinc foil as a counter electrode and a reference electrode, and 2mol/L ZnSO as electrolyte4In the water solution, the electrodeposition voltage interval is 2-3V, the sweep rate is 50mV/s, after 100 cycles of cyclic voltammetry scanning, the solution is washed with deionized water for three times, and is dried for 24 hours at room temperature under the vacuum condition, so that the galvanized carbon fiber flexible cathode is obtained;
(III) preparation of gel electrolyte
(1) 23g of ZnSO4·7H2Adding O into 40ml of deionized water, and stirring to dissolve;
(2) adding 4g of acrylamide into the solution under strong magnetic stirring at 40 ℃;
(3) adding 2mg of N, N' -methylene-bisacrylamide serving as a cross-linking agent and 50mg of ammonium persulfate serving as an initiator into the solution at 40 ℃ under strong magnetic stirring for 0.5 hour to form uncured electrolyte glue;
(IV) preparation of flexible zinc ion hybrid capacitor
And (3) assembling the flexible zinc ion hybrid capacitor according to the sequence of the flexible cathode of the galvanized carbon fiber, the uncured electrolyte glue and the anode of the activated carbon fiber, and keeping the device at 70 ℃ for 2 hours to ensure that the gel electrolyte is completely polymerized to obtain the flexible zinc ion hybrid capacitor. Based on the calculation of the quality of the anode material, the maximum specific capacity of the flexible zinc ion hybrid capacitor is 142 mAh/g.
Example 3
Flexible zinc ion hybrid capacitor based on active carbon fiber (water vapor-potassium hydroxide secondary activation process) anode and galvanized graphene cathode
Preparation of active carbon fiber anode
(1) Placing 0.5g of unactivated commercial carbon fiber sample in a tube furnace, heating to 800 ℃ at a speed of 20 ℃/min under the protection of argon atmosphere, introducing a mixed gas of argon and water vapor (the volume fraction of the water vapor is 0.01%) into the tube furnace for activation for 30min, and reducing to room temperature under the protection of argon to prepare activated carbon fiber (ACF1) which is activated for one time for later use;
(2) soaking 0.1g of the ACF1 in 5mol/L potassium hydroxide solution for 24 hours;
(3) and (3) fully drying the soaked ACF1 in a forced air oven at the temperature of 60 ℃, wherein the mass ratio of ACF1 to potassium hydroxide in the dried product is 1: 4;
(4) activating the ACF1 in the step (3) in a tube furnace at 850 ℃ for 1h in nitrogen atmosphere, wherein the heating rate is 5 ℃/min, repeatedly cleaning the ACF1 with deionized water after cooling until the cleaned solution is neutral, and drying to obtain secondarily activated carbon fibers (ACF2) which are used as the positive electrode of the flexible zinc ion hybrid capacitor;
preparation of (II) zinc-plated graphene flexible negative electrode
(1) The method comprises the steps of adopting a two-electrode device to electrodeposit zinc on the surface of a graphene film by using cyclic voltammetry, specifically taking the graphene film as a working electrode, a zinc foil as a counter electrode and a reference electrode, and an electrolyte of 2mol/L ZnSO4In the water solution, the electrodeposition voltage interval is 2-3V, the sweep rate is 50mV/s, after 100 cycles of cyclic voltammetry scanning, the flexible negative electrode is washed with deionized water for three times, and dried for 24 hours at room temperature under the vacuum condition, so that the flexible negative electrode of the galvanized graphene film is obtained;
(III) preparation of gel electrolyte
(1) 29g of Zn (CF)3SO3)2Adding the mixture into 40ml of deionized water and stirring the mixture to dissolve the mixture;
(2) adding 4g of acrylamide into the solution under strong magnetic stirring at 40 ℃;
(3) adding 2mg of N, N' -methylene-bisacrylamide serving as a cross-linking agent and 50mg of ammonium persulfate serving as an initiator into the solution at 40 ℃ under strong magnetic stirring for 0.5 hour to form uncured electrolyte glue;
(IV) preparation of flexible zinc ion hybrid capacitor
And assembling the flexible zinc ion hybrid capacitor according to the sequence of the flexible cathode of the galvanized graphene, the uncured electrolyte glue and the anode of the activated carbon fiber, and keeping the device at 70 ℃ for 2 hours to ensure that the gel electrolyte is completely polymerized to obtain the flexible zinc ion hybrid capacitor. Based on the mass calculation of the anode material, the maximum specific capacity of the flexible zinc ion hybrid capacitor is 135 mAh/g.
Example 4
Flexible zinc ion hybrid capacitor based on active carbon fiber (water vapor-zinc chloride secondary activation process) anode and galvanized carbon fiber cathode
Preparation of active carbon fiber anode
(1) Placing 0.5g of unactivated commercial carbon fiber sample in a tube furnace, heating to 800 ℃ at a speed of 20 ℃/min under the protection of argon atmosphere, introducing a mixed gas of argon and water vapor (the volume fraction of the water vapor is 0.01%) into the tube furnace for activation for 30min, wherein the flow rate of the water vapor is 1 x 10-4L/min. Reducing the temperature to room temperature under the protection of argon to prepare the active carbon fiber (ACF1) which is activated by water vapor for one time for standby;
(2) 0.1g of ACF1 is soaked in 5mol/L zinc chloride solution for 24 hours;
(3) and (3) fully drying the soaked ACF1 in a forced air oven at the temperature of 60 ℃, wherein the mass ratio of ACF1 to zinc chloride in the dried product is 1: 4.2;
(4) activating the ACF1 in the step (3) in a tube furnace at 900 ℃ for 0.5h in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, repeatedly cleaning the ACF1 with deionized water after cooling until the cleaned solution is neutral, and drying to obtain secondarily activated carbon fibers (ACF2) which are used as the positive electrode of the flexible zinc ion hybrid capacitor;
preparation of (II) galvanized carbon fiber flexible negative electrode
(1) The carbon fibers were soaked in acetone to remove the surface polymer coating, then washed several times with deionized water and ethanol and dried. Adopting a two-electrode device to electrodeposit zinc on the surface of carbon fiber by cyclic voltammetry, specifically taking the carbon fiber as a working electrode, zinc foil as a counter electrode and a reference electrode, and 2mol/L ZnSO as electrolyte4In the water solution, the electrodeposition voltage interval is 2-3V, the sweep rate is 50mV/s, after 100 cycles of cyclic voltammetry scanning, the solution is washed with deionized water for three times, and is dried for 24 hours at room temperature under the vacuum condition, so that the galvanized carbon fiber flexible cathode is obtained;
(III) preparation of gel electrolyte
(1) 23g of ZnSO4·7H2Adding O into 40ml of deionized water, and stirring to dissolve;
(2) adding 4g of acrylamide into the solution under strong magnetic stirring at 40 ℃;
(3) adding 2mg of N, N' -methylene-bisacrylamide serving as a cross-linking agent and 50mg of ammonium persulfate serving as an initiator into the solution at 40 ℃ under strong magnetic stirring for 0.5 hour to form uncured electrolyte glue;
(IV) preparation of flexible zinc ion hybrid capacitor
And assembling the flexible zinc ion hybrid capacitor according to the sequence of the flexible cathode of the galvanized carbon fiber, the uncured electrolyte glue containing zinc salt and the anode of the activated carbon fiber, and keeping the device at 70 ℃ for 2 hours to ensure that the gel electrolyte is completely polymerized to obtain the flexible zinc ion hybrid capacitor. The maximum specific capacity of the flexible zinc ion hybrid capacitor is 115mAh/g calculated based on the mass of the anode material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A flexible zinc ion hybrid capacitor is characterized by comprising a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode adopts flexible self-supporting active carbon fibers with electrochemical activity;
the activated carbon fiber is prepared by adopting a secondary activation process.
2. The flexible zinc ion hybrid capacitor of claim 1, wherein:
the activated carbon fiber is prepared by adopting a secondary activation process, wherein the secondary activation process refers to one of the following three activation processes: (1) firstly, a secondary activation process of water vapor activation and potassium hydroxide activation is carried out; (2) firstly, activating by potassium hydroxide and activating by zinc chloride for the second time; (3) firstly, the secondary activation process of water vapor activation and zinc chloride activation is carried out.
3. The flexible zinc ion hybrid capacitor of claim 2, wherein:
the secondary activation process of firstly carrying out water vapor activation and then carrying out potassium hydroxide activation specifically comprises the following steps:
(1.1) placing the unactivated carbon fiber in a tube furnace, raising the temperature to 600-900 ℃ under the protection of inert gas, then introducing mixed gas of inert gas and water vapor, and activating for 10-60min to obtain the primary activated carbon fiber;
(1.2) soaking the primarily activated carbon fiber in a potassium hydroxide aqueous solution for 2-24h, taking out and drying to obtain a product 1, then placing the product 1 in a 600-900 ℃ tube furnace under a nitrogen atmosphere to activate for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the secondarily activated carbon fiber;
the secondary activation process of firstly activating by potassium hydroxide and then activating by zinc chloride specifically comprises the following steps:
(2.1) placing the unactivated carbon fiber in a potassium hydroxide solution for soaking for 2-24h, taking out and drying to obtain a product 2, placing the product 2 in a tube furnace at the temperature of 600-900 ℃ under an inert atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the once-activated carbon fiber;
(2.2) soaking the primarily activated carbon fiber in a zinc chloride aqueous solution for 2-24h, taking out and drying to obtain a product 3, placing the product 3 in a tube furnace at the temperature of 600-900 ℃ under an inert atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain secondarily activated carbon fiber;
the secondary activation process of firstly carrying out water vapor activation and then carrying out zinc chloride activation specifically comprises the following steps:
(3.1) placing the unactivated carbon fiber in a tube furnace, raising the temperature to 600-900 ℃ under the protection of inert gas, then introducing mixed gas of inert gas and water vapor, and activating for 10-60min to obtain the primary activated carbon fiber;
(3.2) soaking the primarily activated carbon fiber in a zinc chloride aqueous solution for 2-24h, taking out and drying to obtain a product 4, placing the product 4 in a tube furnace with the temperature of 600-900 ℃ under the nitrogen atmosphere for activation for 0.5-2h, then repeatedly cleaning with deionized water until the cleaned solution is neutral, and drying to obtain the secondarily activated carbon fiber.
4. The flexible zinc ion hybrid capacitor of claim 3, wherein:
the volume fraction of the water vapor in the mixed gas of the inert gas and the water vapor in the step (1.1) is 0.001-0.05%; the flow rate of the water vapor was 0.5 x 10-4-1.5*10-4L/min；
The dosage of the potassium hydroxide aqueous solution in the step (1.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the potassium hydroxide in the product 1 is 1:1-1: 5;
the dosage of the potassium hydroxide aqueous solution in the step (2.1) meets the requirement that the mass ratio of the unactivated carbon fiber to the potassium hydroxide in the product 2 is 1:1-1: 5;
the dosage of the zinc chloride aqueous solution in the step (2.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the zinc chloride in the product 3 is 1:1-1: 5;
the volume fraction of the water vapor in the mixed gas of the inert gas and the water vapor in the step (3.1) is 0.001-0.05%; the flow rate of the water vapor was 0.5 x 10-4-1.5*10-4L/min；
The dosage of the zinc chloride aqueous solution in the step (3.2) meets the requirement that the mass ratio of the carbon fiber activated for one time to the zinc chloride in the product 4 is 1:1-1: 5.
5. The flexible zinc ion hybrid capacitor of claim 1, wherein:
the specific surface area of the activated carbon fiber is 500-2500m2/g。
6. The flexible zinc ion hybrid capacitor of claim 1, wherein:
the negative electrode is a galvanized flexible substrate, or a zinc wire is directly used as the negative electrode of the flexible zinc ion hybrid capacitor;
the electrolyte is a gel electrolyte system containing zinc salt, wherein the zinc salt is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc trifluoromethanesulfonate and bis (trifluoromethylsulfonyl) imide zinc.
7. The flexible zinc ion hybrid capacitor of claim 6, wherein:
the zinc-plated flexible substrate is obtained by electrodepositing zinc on a fibrous or film-shaped flexible substrate by using a cyclic voltammetry through a two-electrode device, and specifically comprises the following steps: using a fibrous or film-shaped flexible substrate as a working electrode, a zinc foil as a counter electrode and a reference electrode, and 0.1-3mol/L ZnSO as electrolyte4And (3) carrying out water solution electrodeposition with the voltage interval of 2-3V and the sweep rate of 2-200mV/s, carrying out cyclic voltammetry scanning for 10-200 circles, washing with water, and then drying to obtain the galvanized flexible substrate negative electrode material.
8. The flexible zinc ion hybrid capacitor of claim 7, wherein:
the flexible substrate is a substrate formed by at least one of carbon fiber, carbon nanofiber, carbon nanotube, graphene and graphite alkyne materials.
9. A method of making a flexible zinc ion hybrid capacitor according to any one of claims 1 to 8 comprising the steps of:
(1) preparing a zinc salt into 0.1-3mol/L aqueous solution, adding the aqueous solution containing a monomer, a cross-linking agent and an initiator under the stirring condition for crosslinking for 10-30min, or adding the aqueous solution containing gel in a swelling state under the stirring condition to form uncured electrolyte glue;
(2) and assembling the flexible zinc ion hybrid capacitor according to the sequence of the cathode, the uncured gel electrolyte glue containing the zinc salt and the anode, and obtaining the flexible zinc ion hybrid capacitor after the gel electrolyte is completely polymerized.
10. Use of a flexible zinc ion hybrid capacitor according to any one of claims 1 to 8 in the field of flexible energy storage and portable, wearable electronics.
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