CN114121496A - Flexible composite electrode, preparation method thereof and flexible energy storage device - Google Patents

Flexible composite electrode, preparation method thereof and flexible energy storage device Download PDF

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Publication number
CN114121496A
CN114121496A CN202111266959.6A CN202111266959A CN114121496A CN 114121496 A CN114121496 A CN 114121496A CN 202111266959 A CN202111266959 A CN 202111266959A CN 114121496 A CN114121496 A CN 114121496A
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electrode
flexible
flexible composite
composite electrode
electrolyte
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薛冬峰
陈昆峰
孙向飞
王晓明
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2021/137308 priority patent/WO2023070856A1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The application belongs to the technical field of capacitors, and particularly relates to a flexible composite electrode, a preparation method of the flexible composite electrode, and a flexible energy storage device. The preparation method of the flexible composite electrode comprises the following steps: dissolving an electrochemical polymerization monomer and a flexible reinforcement in a solvent to obtain an electrolyte; and constructing an electrode system, adding the electrolyte into the electrode system, carrying out an electrolytic reaction, forming a flexible composite film on the surface of the working electrode, and separating to obtain the flexible composite electrode. According to the preparation method of the flexible composite electrode, the flexible composite electrode of the polymer matrix and the flexible reinforcer can be synthesized by a one-step electrolysis method, the process is simple, the preparation condition is mild, and the preparation method is suitable for industrial large-scale production and application; the size of the prepared flexible composite electrode can be flexibly regulated and controlled, and the working electrode with the corresponding size can be selected according to different application requirements, so that the composite electrode with excellent flexibility and flexibility can be efficiently synthesized, and the composite electrode is particularly suitable for a miniature flexible energy storage device.

Description

Flexible composite electrode, preparation method thereof and flexible energy storage device
Technical Field
The application belongs to the technical field of capacitors, and particularly relates to a flexible composite electrode, a preparation method of the flexible composite electrode, and a flexible energy storage device.
Background
With the rapid development of small-scale microelectronics, various applications such as wearable sensors, epidermal electronics, and nano robots are increasingly demanding portable or implantable microsystems. The rapid development of ultra-thin, ultra-light portable electronic devices is limited by the development of small energy storage devices. One approach to addressing this challenge is to fabricate miniature energy storage devices of high energy density, flexible design and long life. At present, most micro devices rely on batteries to provide the required energy and power, and it is becoming very important to develop power devices capable of powering small microelectronic devices. Micro supercapacitors, with sufficient power density and fast frequency response, are the first choice for advanced miniaturized energy storage devices. Especially miniature flexible supercapacitors, have high power and energy density, high rate capability and cycling stability, which makes them very attractive for future electronic applications. However, the relatively poor power supply handling capability and limited battery life prevent their applicability to systems requiring high current peaks.
At present, the preparation methods for the flexible electrode mainly include: metal organic compound vapor deposition, sol-gel, catalytic chemical vapor deposition, metal organic compound thermal decomposition, plasma enhanced chemical vapor deposition, liquid source atomization chemical deposition, pulsed laser deposition, suction filtration, shot method, and the like. These methods have certain disadvantages in terms of equipment, technical requirements and the like.
Disclosure of Invention
The application aims to provide a flexible composite electrode, a preparation method thereof and a flexible energy storage device, and aims to solve the technical problems that the preparation method of the flexible electrode in the existing miniature flexible super capacitor is complex and large-area flexible electrode preparation is difficult to realize to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a flexible composite electrode, comprising the steps of:
dissolving an electrochemical polymerization monomer and a flexible reinforcement in a solvent to obtain an electrolyte;
and constructing an electrode system, adding the electrolyte into the electrode system, carrying out an electrolytic reaction, forming a flexible composite film on the surface of the working electrode, and separating to obtain the flexible composite electrode.
Further, the conditions of the electrolytic reaction include: electrolyzing for 10-30 minutes under the condition of 10-15V of voltage.
Further, a conductive agent is added to the electrolyte.
Further, the electrochemical polymerization monomer is selected from at least one of pyrrole, aniline and thiophene.
Further, the flexibility reinforcement is selected from Ti2C. At least one of graphene, carbon nanospheres, and carbon nanotubes.
Further, the conductive agent is selected from at least one of sodium benzene sulfonate, sodium p-toluene sulfonate, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
Furthermore, in the electrolyte, the concentration of the electrochemical polymerization monomer is 8-10 mg/mL, the concentration of the flexibility enhancer is 0.5-1.5 mg/mL, and the concentration of the conductive agent is 4-6 mg/mL.
Further, the solvent in the electrolyte is selected from water.
Further, the electrode system is selected from a three-electrode system including a working electrode, a counter electrode, and a reference electrode.
Further, the working electrode is selected from one of an inert metal sheet, a conductive glass sheet and a carbon electrode sheet;
further, the counter electrode is selected from one of a platinum counter electrode and a carbon counter electrode.
Further, the reference electrode is selected from a saturated calomel electrode, an Ag/AgCl electrode, an Hg/HgO electrode and an Hg/Hg electrode2SO4One of the electrodes.
In a second aspect, the present application provides a flexible composite electrode prepared by the above method, the flexible composite electrode comprising a flexible polymer matrix and a flexibility enhancer in-situ doped in the flexible polymer matrix.
Further, the flexible composite electrode is doped with a conductive reinforcing agent.
Further, in the flexible composite electrode, the mass ratio of the flexible polymer matrix to the flexible reinforcement is (8-10): (0.5 to 1.5).
In a third aspect, the present application provides a flexible energy storage device, where the flexible energy storage device includes the flexible composite electrode prepared by the above method, or includes the above flexible composite electrode.
According to the preparation method of the flexible composite electrode provided by the first aspect of the application, the flexible composite electrode of the polymer matrix and the flexible reinforcer can be synthesized through a one-step electrolysis method, an initiator does not need to be additionally added, the preparation method does not need to be carried out under harsh conditions, the process is simple, the preparation conditions are mild, and the preparation method is suitable for industrial large-scale production and application. The size of the prepared flexible composite electrode can be flexibly regulated, the working electrode with the corresponding size is selected according to different application requirements, the large-size flexible composite electrode can be prepared on the surface of the working electrode, the composite electrode is excellent in flexibility and flexibility, and the composite electrode can be widely applied to flexible energy storage devices as an electrode material, especially miniature flexible capacitors.
The flexible composite electrode provided by the second aspect of the application is synthesized by the method in one step and comprises a flexible polymer matrix and a flexible reinforcement doped in the flexible polymer matrix in situ, so that the flexible reinforcement in the flexible composite electrode and the flexible polymer matrix have good combination stability, the flexibility of the composite electrode is effectively enhanced, the flexible composite electrode with the size can be obtained, and the flexibility and the feasibility of the flexible composite electrode as an electrode material applied to a flexible energy storage device are improved.
The flexible energy storage device provided by the third aspect of the application comprises the flexible composite electrode, so that the composite electrode is good in stability and excellent in flexibility, can be bent to any radian, meets the application requirements of flexible energy storage devices of different systems, and improves the stability of the electrochemical performance of the device.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for manufacturing a flexible composite electrode provided in an embodiment of the present application;
FIG. 2 is a schematic view of an electrolyte apparatus provided in example 1 of the present application;
FIG. 3 is a topographical view of a flexible composite electrode provided in example 1 of the present application;
FIG. 4 is a graph of a bending test of a flexible composite electrode provided in example 2 of the present application;
fig. 5 is a three-electrode charging and discharging curve diagram of the flexible composite electrode provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for manufacturing a flexible composite electrode, including the following steps:
s10, dissolving an electrochemical polymerization monomer and a flexible reinforcement in a solvent to obtain electrolyte;
s20, constructing an electrode system, adding electrolyte into the electrode system, carrying out an electrolytic reaction, forming a flexible composite film on the surface of the working electrode, and separating to obtain the flexible composite electrode.
According to the preparation method of the flexible composite electrode provided by the first aspect of the embodiment of the application, the mixed solution of the electrochemical polymerization monomer and the flexible reinforcement is used as an electrolyte, an electrolytic reaction is carried out in an electrode system, and under the action of an electric field, the potential of the working electrode provides energy required by the polymerization reaction for the electrochemical polymerization monomer, so that the monomer loses electrons on the surface of the electrode and is polymerized to form a flexible polymer matrix. Meanwhile, the flexible reinforcer in the electrolyte is adsorbed and combined in the flexible polymer matrix, a flexible composite film of the flexible polymer matrix and the flexible reinforcer is formed on the surface of the working electrode, and the flexibility of the film can be effectively improved by doping the flexible reinforcer. And separating the flexible composite film from the surface of the electrode to obtain the flexible composite electrode. According to the preparation method of the flexible composite electrode, the flexible composite electrode of the polymer matrix and the flexible reinforcer can be synthesized through a one-step electrolysis method, an initiator does not need to be added additionally, the preparation method does not need to be carried out under harsh conditions, the process is simple, the preparation conditions are mild, and the preparation method is suitable for industrial large-scale production and application. The size of the prepared flexible composite electrode can be flexibly regulated, the working electrode with the corresponding size is selected according to different application requirements, the large-size flexible composite electrode can be prepared on the surface of the working electrode, the composite electrode is excellent in flexibility and flexibility, and the composite electrode can be widely applied to flexible energy storage devices as an electrode material, especially miniature flexible capacitors.
In some embodiments, in step S10, a conductive agent is further added to the electrolyte, and during the process of forming the flexible polymer matrix by electrochemical polymerization of the electrochemical polymerization monomer losing electrons on the surface of the electrode, the conductive agent can be incorporated into the flexible polymer matrix, so as to further improve the conductive performance of the flexible composite electrode and improve the electron transfer and transport efficiency.
In some embodiments, the conductive agent is selected from at least one of sodium benzene sulfonate, sodium p-toluene sulfonate, sodium dodecyl sulfonate, and sodium dodecyl benzene sulfonate. Further, the conductive agent is preferably sodium p-toluenesulfonate. The conductive agents can enhance the conductivity of the flexible composite electrode, improve the electron transfer transmission efficiency, accelerate the polymerization rate of electrochemical polymerization monomers, improve the monomer polymerization efficiency and shorten the reaction time. In some embodiments, the conductive agent is preferably sodium p-toluenesulfonate, which can accelerate the polymerization of electrochemical polymerization monomers such as pyrrole and the like, reduce the formation time of the flexible composite electrode film, and simultaneously, the sodium p-toluenesulfonate is doped into the flexible composite electrode, so that the conductivity of the electrode can be effectively enhanced.
In some embodiments, the electrochemically polymerizable monomer is selected from at least one of pyrrole, aniline, thiophene in the electrolyte. Further, pyrrole is preferable as the electrochemically polymerizable monomer. Under the action of an electric field, the potential of a working electrode of the electrochemical polymerization monomers can provide required energy for monomer polymerization, monomer molecules are subjected to electron removal on the surface of the working electrode under the action of the electric field to form cationic free radicals, and the monomer free radicals are mutually combined and form a flexible polymer matrix through chain growth. In some embodiments, the electrochemical polymerization monomer is preferably pyrrole, firstly, pyrrole monomer molecules lose electrons on the surface of the working electrode under the action of an electric field to form cationic free radicals, then the free radicals are combined with other pyrrole monomers to form pyrrole dimers, and finally, a polypyrrole macromolecular chain is obtained through a chain growth step, and a flexible polymer thin film layer is formed on the surface of the working electrode.
In some embodiments, the flexibility enhancer in the electrolyte is selected from Ti2C. At least one of graphene, carbon nanospheres, carbon nanotubes; when the materials are added into the composite electrode, the flexibility of the composite electrode film can be enhanced, and the composite electrode film also has excellent electrochemical performance. Thus, these preferred flexibility enhancers can increase not only the flexibility of the flexible composite electrode, but also the electrochemical properties of the flexible composite electrode. In some embodiments, the flexibility enhancer is selected from Ti2C,Ti2C surfaceContains a large amount of negative charges, can be adsorbed in a flexible polymer matrix on the surface of the working electrode, has good combination stability with the polymer matrix, and improves the stability and flexibility of the flexible composite film. In addition, Ti2The C has high volume specific capacity, metal-grade conductivity, good hydrophilicity and abundant surface chemical activity, and can improve the electrochemical properties such as specific capacity, rate capability and the like of the flexible composite electrode.
In some embodiments, the concentration of the electrochemically polymerizable monomer in the electrolyte is 8-10 mg/mL, the concentration of the flexibility enhancer is 0.5-1.5 mg/mL, and the concentration of the conductive agent is 4-6 mg/mL. The concentrations of the electrochemical polymerization monomer, the flexible reinforcer and the conductive agent in the electrolyte in the embodiment of the application can influence the doping contents of the flexible reinforcer and the conductive agent in the prepared flexible composite electrode and influence the formation of the flexible composite film. If the concentrations of the flexible reinforcer and the conductive agent are too low and the concentration of the electrochemical polymerization monomer is too high, the flexible reinforcer and the conductive agent are not favorably doped into the polymer film matrix; if the concentration of the electrochemical polymerization monomer is too low and the concentrations of the flexible reinforcer and the conductive agent are too high, the polymerization of the monomer is influenced, the polymerization efficiency of the monomer is reduced, the formation of a polymer film matrix is influenced, and a complete flexible composite film with excellent performance is difficult to form on the surface of the working electrode. In some embodiments, the concentration of electrochemically polymerized monomers in the electrolyte includes, but is not limited to, 8mg/mL, 8.5mg/mL, 9mg/mL, 9.5mg/mL, 10mg/mL, and the like, the concentration of flexibility enhancer includes, but is not limited to, 0.5mg/mL, 0.8mg/mL, 1mg/mL, 1.2mg/mL, 1.5mg/mL, and the like, and the concentration of conductive agent is 4mg/mL, 4.5mg/mL, 5mg/mL, 5.5mg/mL, 6mg/mL, and the like.
In some embodiments, the solvent in the electrolyte is selected from at least one of water and ethanol, and the solvent has better solubility for the electrochemical polymerization monomer, the flexibility enhancer and the conductive agent, so as to provide a solution environment for the electrolysis reaction. In some embodiments, the solvent in the electrolyte may be water alone, ethanol alone, or a mixed solution of water and ethanol.
In some embodiments, a method of formulating an electrolyte includes the steps of: firstly, dissolving the flexible reinforcement in a solvent, then adding an electrochemical polymerization monomer and a conductive agent for mixing treatment again to obtain the electrolyte with good dispersion stability.
In some embodiments, the electrochemically polymerizable monomer is pyrrole and the flexibility enhancer is Ti2C, the conductive agent adopts sodium p-toluenesulfonate, and the electrolyte is prepared by the following steps of: mixing Ti2Dispersing C in a solvent, and carrying out ultrasonic treatment for 1-3 hours in an inert atmosphere to ensure that Ti is2C is sufficiently dissolved in the solvent and prevents Ti2C is oxidized to improve stability. Then adding sodium p-toluenesulfonate and pyrrole for mixing to form stable electrolyte.
In some embodiments, the electrode system constructed in step S20 may be a three-electrode system, or may be a two-electrode system, and in some embodiments, the electrode system is selected from a three-electrode system including a working electrode, a counter electrode, and a reference electrode. Compared with a two-electrode system, the three-electrode system has one more reference electrode, and the potential control of the working electrode is more accurate.
In some embodiments, the working electrode is selected from one of an inert metal sheet, a conductive glass sheet, a carbon electrode sheet. In some embodiments, the inert metal sheet comprises a platinum sheet, a gold sheet, a silver sheet, a titanium sheet, a nickel sheet, a stainless steel sheet, or the like, the conductive glass sheet comprises an FTO sheet, an ITO sheet, or the like, and the carbon electrode sheet comprises a graphite sheet electrode sheet, a glassy carbon electrode sheet, or the like. The working electrode adopted in the embodiment of the application can provide energy for the polymerization reaction of electrochemical polymerization monomers in the electrolytic process, so that the monomers lose electrons under the action of an electric field to become cationic free radicals, and the polymerization between the monomers is facilitated to form a polymer film. In some embodiments, the working electrode is a titanium sheet, the titanium sheet is used as the working electrode in the electrolysis process, the titanium sheet has good stability, can be recycled, and meanwhile, the area can be manually controlled.
In some embodiments, the counter electrode is selected from one of a platinum counter electrode and a carbon counter electrode, and the counter electrode and the working electrode can form a series circuit to conduct electricity.
In some embodiments, the reference electrode is selected from the group consisting ofAnd Calomel Electrode (SCE), Ag/AgCl electrode, Hg/HgO electrode, Hg/Hg2SO4One of the electrodes. The electrode potentials of these reference electrodes are known and stable, i.e. the exchange current density of the electrode process is rather high, being non-or poorly polarized, the thermodynamic equilibrium potential can be established quickly, and the electrolyte in these reference electrodes does not react with the electrolyte or related substances in the electrolytic cell, the temperature coefficient of the electrode potentials is small. In addition, the electrolyte ions in the reference electrodes penetrate into the solution without affecting the polymerization of the electrochemically polymerized monomers on the surface of the working electrode to form a flexible polymer matrix.
In some embodiments, the conditions of the electrolysis reaction include: electrolyzing for 10-30 minutes under the condition of 10-15V of voltage. The voltage of the electrolytic reaction is 10-15V, the voltage is beneficial to the working electrode to provide energy for the polymerization of electrochemical polymerization monomers, so that the polymer monomers lose electrons on the surface of the working electrode and become cationic free radicals, and the polymer matrix film is formed by polymerization and chain growth of the monomer free radicals. The time of the electrolytic reaction can be determined according to the thickness of the flexible composite electrode to be prepared, and if the flexible composite electrode with high thickness and large size needs to be prepared, the electrolytic time can be prolonged. In some embodiments, the flexible composite electrode obtained by electrolyzing for 10-30 minutes under the condition of 10-15V has a proper size and is applicable to various flexible devices such as a micro flexible capacitor and the like. In some embodiments, the voltage of the electrolysis reaction includes, but is not limited to, 10V, 11V, 12V, 13V, 14V, 15V, and the like, and the electrolysis time includes, but is not limited to, 10 minutes, 12 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, and the like.
In some embodiments, a method of making a flexible composite electrode includes the steps of:
s11, adopting pyrrole as an electrochemical polymerization monomer and Ti as a flexible reinforcement2C, the conductive agent adopts sodium p-toluenesulfonate, and the electrolyte is prepared by the following steps of: mixing Ti2Dispersing C in a solvent, and carrying out ultrasonic treatment for 1-3 hours in an inert atmosphere to ensure that Ti is2C is sufficiently dissolved in the solvent and prevents Ti2C is oxidized, and then the reaction solution is oxidized,the stability is improved. Then adding sodium p-toluenesulfonate and pyrrole for mixing to form stable electrolyte.
S21, respectively taking (Ag/AgCl)/V, a titanium sheet and a platinum sheet as a reference electrode, a working electrode and a counter electrode to construct a three-electrode system, adding electrolyte into an electrolyte tank, electrolyzing for 10-30 minutes under the condition that the voltage is 10-15V to form a flexible composite film on the surface of the working electrode, and separating to obtain the flexible composite electrode.
In a second aspect, the present embodiments provide a flexible composite electrode prepared by the above method, where the flexible composite electrode includes a flexible polymer matrix and a flexible reinforcement doped in situ in the flexible polymer matrix.
The flexible composite electrode provided by the second aspect of the embodiment of the application is synthesized by the method in one step and comprises a flexible polymer matrix and a flexible reinforcement doped in the flexible polymer matrix in situ, so that the flexible reinforcement in the flexible composite electrode and the flexible polymer matrix have good combination stability, the flexibility of the composite electrode is effectively enhanced, the flexible composite electrode with the size can be obtained, and the flexibility and the feasibility of the flexible composite electrode as an electrode material applied to a flexible energy storage device are improved.
In some embodiments, the flexible composite electrode is further doped with a conductivity enhancer; by further doping the conductive reinforcing agent, the conductivity of the flexible composite electrode is improved, and the electron transfer transmission efficiency of the electrode is improved.
In some embodiments, in the flexible composite electrode, the mass ratio of the flexible polymer matrix to the flexible reinforcement is (8-10): (0.5-1.5), and the mass ratio effectively ensures the stability, flexibility and conductivity of the flexible composite electrode. If the content of the flexible polymer matrix is too low, the stability of the flexible composite electrode is reduced, and if the content of the flexible reinforcement is too low, the flexibility and the conductivity of the flexible composite electrode are reduced. In some embodiments, in the flexible composite electrode, the mass ratio of the flexible polymer matrix to the flexible reinforcement includes, but is not limited to (8-9): (0.5 to 1.5), (9 to 101): (0.5-1.5), (8-9): (0.5-1), (9-10): (0.5-1), (8-9): (1-1.5), (9-10): (1-1.5), preferably (8.5-9): (0.6-1).
In a third aspect of the embodiments of the present application, a flexible energy storage device is provided, where the flexible energy storage device includes the flexible composite electrode prepared by the above method, or includes the flexible composite electrode.
The flexible energy storage device provided by the third aspect of the embodiment of the application comprises the flexible composite electrode, so that the composite electrode has good stability and excellent flexibility, can be bent to any radian, meets the application requirements of flexible energy storage devices of different systems, and improves the stability of the electrochemical performance of the device.
The flexible energy storage device of the embodiment of the application includes but is not limited to a miniature flexible capacitor.
In order to clearly understand the details of the above implementation and operation of the present application and to obviously show the advanced performance of the flexible energy storage device and the manufacturing method thereof according to the embodiments of the present application, the above technical solution is illustrated by a plurality of embodiments.
Example 1
A flexible composite electrode, prepared by the steps of:
adding 5mg of Ti2Dispersing C-MXene in 40mL of deionized water, carrying out ultrasonic treatment for 2 hours under Ar flow to form a uniform mixed solution, adding 0.355g of pyrrole and 0.955g of sodium p-toluenesulfonate into the mixed solution, and uniformly mixing to obtain an electrolyte;
and (Ag/AgCl)/V, a titanium sheet and a platinum sheet are respectively used as a reference electrode, a working electrode and a counter electrode to construct a three-electrode system, as shown in the attached figure 2. The deposition was carried out for 1200s by a constant voltage method at 10V. After electrodeposition, Ti2The C/PPy composite membrane is taken off from the working electrode titanium sheet, and Ti is carefully washed2And removing adsorbed substances from the C/PPy composite membrane and drying at room temperature to obtain the flexible composite electrode.
Example 2
A flexible composite electrode, prepared by the steps of:
mixing 10mg of Ti2C-MXene was dispersed in 40mL of ethanol and after sonication for 2 hours under Ar flow to form a homogeneous mixed solution, 0 was added.355g of pyrrole and 0.955g of sodium p-toluenesulfonate are added into the mixed solution and mixed uniformly to obtain electrolyte;
and (Ag/AgCl)/V, a titanium sheet and a platinum sheet are respectively used as a reference electrode, a working electrode and a counter electrode to construct a three-electrode system, and a constant voltage method is used, wherein the voltage is 10V, and the deposition time is 800 s. After electrodeposition, Ti2The C/PPy composite membrane is taken off from the working electrode titanium sheet, and Ti is carefully washed2And removing adsorbed substances from the C/PPy composite membrane and drying at room temperature to obtain the flexible composite electrode.
Further, in order to verify the progress of the examples of the present application, the following performance tests were performed on the flexible composite electrode prepared in the examples:
1. the morphology machine of the flexible composite electrode prepared in the embodiment 1 is observed, and as shown in the attached drawing 2, the flexible composite electrode prepared in the embodiment 1 is complete in film layer and large in size.
2. The flexibility of the flexible composite electrode prepared in example 2 was tested, and as shown in fig. 3, the flexible composite electrode film prepared in example 2 can be bent to any radian, and can be substantially folded at 180 ° in half, and the flexible composite electrode shows excellent flexibility.
3. The flexible composite electrode prepared in the embodiment 1 is used as a working electrode, a platinum sheet is used as a counter electrode, Ag/AgCl)/V is used as a reference electrode, three-electrode charging and discharging tests are carried out, the test result is shown in figure 4, and the test chart shows that the capacity measured under different current densities of the flexible composite electrode prepared in the embodiment of the application is basically maintained unchanged, the capacity stability is good, the rate capability is excellent, and the application requirements of different devices on the rate capability can be met.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A preparation method of a flexible composite electrode is characterized by comprising the following steps:
dissolving an electrochemical polymerization monomer and a flexible reinforcement in a solvent to obtain an electrolyte;
and constructing an electrode system, adding the electrolyte into the electrode system, carrying out an electrolytic reaction, forming a flexible composite film on the surface of the working electrode, and separating to obtain the flexible composite electrode.
2. The method of making a flexible composite electrode according to claim 1, wherein the conditions of the electrolysis reaction comprise: electrolyzing for 10-30 minutes under the condition of 10-15V of voltage.
3. The method for preparing a flexible composite electrode according to claim 1 or 2, wherein a conductive agent is further added to the electrolyte.
4. The method for preparing a flexible composite electrode according to claim 3, wherein the electrochemical polymerization monomer is at least one selected from pyrrole, aniline and thiophene;
and/or, the flexibility reinforcement is selected from Ti2C. At least one of graphene, carbon nanospheres, carbon nanotubes;
and/or the conductive agent is selected from at least one of sodium benzene sulfonate, sodium p-toluene sulfonate, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
5. The preparation method of the flexible composite electrode according to claim 3, wherein in the electrolyte, the concentration of the electrochemical polymerization monomer is 8-10 mg/mL, the concentration of the flexibility enhancer is 0.5-1.5 mg/mL, and the concentration of the conductive agent is 4-6 mg/mL;
and/or, the solvent in the electrolyte is selected from water.
6. The method of making a flexible composite electrode according to any one of claims 1, 2, 4 or 5, wherein the electrode system is selected from a three-electrode system comprising a working electrode, a counter electrode and a reference electrode.
7. The method of claim 6, wherein the working electrode is selected from one of an inert metal sheet, a conductive glass sheet, and a carbon electrode sheet;
and/or the counter electrode is selected from one of a platinum counter electrode and a carbon counter electrode;
and/or the reference electrode is selected from a saturated calomel electrode, an Ag/AgCl electrode, an Hg/HgO electrode and an Hg/Hg electrode2SO4One of the electrodes.
8. A flexible composite electrode prepared according to any one of claims 1 to 7, comprising a flexible polymer matrix and a flexibility enhancer in situ doped in the flexible polymer matrix.
9. The flexible composite electrode of claim 8, further doped with a conductivity enhancer;
and/or in the flexible composite electrode, the mass ratio of the flexible polymer matrix to the flexible reinforcer is (8-10): (0.5 to 1.5).
10. A flexible energy storage device, characterized in that the flexible energy storage device comprises a flexible composite electrode prepared by the method of any one of claims 1 to 7 or comprises a flexible composite electrode of any one of claims 8 to 9.
CN202111266959.6A 2021-10-28 2021-10-28 Flexible composite electrode, preparation method thereof and flexible energy storage device Pending CN114121496A (en)

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