CN114566390B - Self-adaptive electrode material pore structure remolding method, electrode material and application thereof - Google Patents

Self-adaptive electrode material pore structure remolding method, electrode material and application thereof Download PDF

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CN114566390B
CN114566390B CN202210068021.1A CN202210068021A CN114566390B CN 114566390 B CN114566390 B CN 114566390B CN 202210068021 A CN202210068021 A CN 202210068021A CN 114566390 B CN114566390 B CN 114566390B
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electrode material
sodium
pore structure
aluminum
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CN114566390A (en
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曲良体
马鸿云
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Tsinghua University
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    • 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
    • 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
    • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin

Abstract

The invention discloses a self-adaptive electrode material pore structure remodeling method, an electrode material and application thereof. The method comprises the following steps: (1) Mixing a nano active material, a conductive agent, a binder and a dispersing agent to obtain an electrode slurry; (2) Loading electrode slurry on the surface of a current collector so as to obtain an electrode; (3) The electrode is used as a working electrode, a counter electrode and a reference electrode are connected, a three-electrode electrochemical system is assembled in an active electrolyte, electrochemical scanning is carried out in a certain potential interval, and cations and/or anions in the active electrolyte are inserted into and taken out of characteristic holes of the working electrode under the drive of an electric field so as to reshape the hole structure of an electrode material. Therefore, the pore structure of the electrode material remolded by the method can effectively contain solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is stored most densely, so that the electrode material exhibits an ultra-high charge storage density.

Description

Self-adaptive electrode material pore structure remolding method, electrode material and application thereof
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a self-adaptive electrode material pore structure remodeling method, an electrode material and application thereof.
Background
The large-scale application of new energy sources such as solar energy, wind energy and the like puts higher demands on the design and development of future electrochemical energy storage devices, which should have higher energy density, faster charging speed, longer cycle life and lower manufacturing cost. However, the current electrochemical energy storage devices still have lower energy conversion efficiency, poorer cycling stability and slower charge and discharge speeds.
Thus, the performance of existing electrochemical energy storage devices remains to be improved.
Disclosure of Invention
The present application is primarily based on the following problems and findings:
to achieve the above object, the inventors have found that different electrochemistry can be performed from the viewpoint of electrochemical energy storage mechanismThe chemical system is used for screening, compared with monovalent carriers (such as Li + 、Na + 、K + ) And divalent carriers (e.g. Mg 2+ 、Zn 2+ 、Ca 2 + ) In terms of trivalent carriers (e.g. Al 3+ ) With higher charge density, the corresponding electrochemical energy storage device also has higher theoretical capacity. Therefore, from the theoretical and experimental points of view, a great deal of work is being carried out on the development of high-performance aluminum ion batteries.
However, the current aluminum ion battery still has the problems of lower energy conversion efficiency, poorer cycle stability, slower charge and discharge speed and the like, and the problems are that the aluminum ion battery is formed by Al 3+ Caused by a strong electrostatic field around, the stronger electrostatic field causes Al 3+ And the solvent molecules in the electrolyte and the host electrode have strong interactions. This results in Al 3+ The desolvation process at the electrode/electrolyte interface is very slow, also resulting in desolvated Al 3+ Transport within the electrode material is very difficult. Thereby shielding Al 3+ The ultra-strong electrostatic field around is the key for realizing the efficient storage of the aluminum ion-based electrochemical energy storage device, and is also an effective way for constructing the high-performance aluminum ion-based electrochemical energy storage device.
The inventors have found that the simplest and most effective method of shielding the electrostatic field around a bare ion is to introduce a solvated shell around it, i.e. using solvated Al 3+ As carriers. When solvated Al is used 3+ As carriers, the electrochemical energy storage mechanism of the corresponding energy storage device is converted into a rapid capacitive process. The capacitive energy storage mechanism can provide the device with energy conversion efficiency close to 100%, excellent cycling stability and ultra-fast charge and discharge speeds. Although the energy storage device has many of the above advantages, solvated Al 3+ Having a large hydration radius (0.475 nm) and a high desolvation energy (4525 kJ/mol), these characteristics impose higher demands on the pore structure of the electrode material, i.e., to achieve Al 3+ The electrode material should have a characteristic hole large enough to accommodate large-sized Al 3+ At the same time, in order to ensure high charge storage density, the electrode material should also haveThere is a dense ordered microstructure, however none of the existing capacitive electrode materials possess these characteristics. Thus, to achieve solvation of Al 3+ Is to design and construct and solvate Al 3+ Highly matched electrode materials are highly necessary.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a method for remodeling the pore structure of an electrode material, an electrode material and application thereof, wherein the pore structure of the electrode material remolded by the method can effectively accommodate solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the electrode material shows the ultrahigh charge storage density, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the traditional capacitance material is solved.
In one aspect of the invention, the invention provides a method for adaptively remolding the pore structure of an electrode material. According to an embodiment of the invention, the method comprises: (1) Mixing a nano active material, a conductive agent, a binder and a dispersing agent to obtain an electrode slurry; (2) Loading the electrode slurry on the surface of a current collector so as to obtain an electrode; (3) And the electrode is used as a working electrode and is connected with a counter electrode and a reference electrode, a three-electrode electrochemical system is assembled in an active electrolyte, electrochemical scanning is carried out in a certain potential interval, and cations and/or anions in the active electrolyte are inserted into and removed from characteristic holes of the working electrode under the drive of an electric field so as to reshape the hole structure of the electrode material.
The inventors found that by loading an electrode slurry comprising a nano-active material, a conductive agent, a binder and a dispersant on the surface of a current collector to obtain an electrode as a working electrode, and connecting a counter electrode and a reference electrode, a three-electrode electrochemical system is assembled in an active electrolyte and electrochemical scanning is performed in a certain potential interval, and cations and/or anions in the active electrolyte are charged under the drive of an electric field forceWhen ions with the supporting column function are circularly embedded into and separated from characteristic holes of the electrode material, the electrode material is enabled to complete self-adaptive remodeling of the characteristic holes while continuously adapting to the ion storage requirement, and the remodeled hole structure in the obtained electrode material can effectively accommodate solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the charge storage density of the electrode material is effectively improved, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the electrode material in the prior art is solved; meanwhile, the remolding method has good universality, can realize the remolding of the pore structure of various nano active materials, further provides a rich material system for the construction of high-performance energy storage devices, and has important scientific value and practical significance for further developing the high-performance energy storage devices; in addition, the electrode preparation method in the method has mature process route, has good compatibility with various electrode materials and production processes, has good compatibility with related technologies in the electroplating and electrolysis industries in the electrochemical self-adaptive pore structure remodeling process used in the method, can finish the electrode material characteristic pore structure remodeling process by using the production process in the electroplating and electrolysis industries, has low cost and is easy for large-scale production. Therefore, the method is simple and convenient to operate, repeatable, low in cost and easy to realize and realize large-scale production, and the electrode material obtained by adopting the method has a pore structure capable of effectively accommodating large-size solvated Al 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is stored most densely, so that the electrode material exhibits an ultra-high charge storage density.
In addition, the method for remolding the pore structure of the self-adaptive electrode material according to the embodiment of the invention can also have the following additional technical characteristics:
according to an embodiment of the present invention, in step (1), the nano-active material comprises graphene, graphite alkyne, molybdenum disulfide, hexagonal boron nitride, graphite phase C 3 N 4 At least one of black phosphazene, silylene oxide, two-dimensional transition metal carbonitride. Therefore, the method not only has good universality, but also can lead the finally prepared electrode material to have higher charge storage density.
According to an embodiment of the present invention, in step (1), the conductive agent includes at least one of conductive carbon black, acetylene black, ketjen black, single-layer graphene nanoplatelets, single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphite powder. Therefore, the conductive agent not only has better chemical corrosion resistance, but also can lead the prepared electrode material to have better conductivity.
According to an embodiment of the present invention, in step (1), the binder includes at least one of polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyethylene oxide, and sodium alginate. Therefore, the mechanical stability of the prepared electrode material can be further improved, and further, the charge storage density of the electrode material can be improved more favorably.
According to an embodiment of the present invention, in step (1), the dispersant includes at least one of water, ethanol, ethylene glycol, acetone, acetonitrile, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide, and dimethylsulfoxide. Therefore, the dissolution and dispersion effects with high efficiency and low cost can be achieved at the same time.
According to an embodiment of the present invention, in step (2), the current collector includes at least one of copper foil, aluminum foil, titanium foil, nickel foil, graphite foil, gold sheet, platinum sheet, stainless steel strip, stainless steel mesh, nickel foam, copper foam, carbon cloth, and carbon paper. Thus, the preparation of the electrode is facilitated, and the prepared electrode has lower quality and better mechanical property.
According to an embodiment of the present invention, in step (3), the active electrolyte comprises a solute and a solvent, wherein the solute comprises at least one anion or cation having a size between that of a solvated metal ion and the characteristic pores, wherein the solvated metal ion comprises Al 3+ 、Mg 2+ And Ca 2+ At least one of them. Thereby, the characteristic holes on the obtained electrode material can effectively contain solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma performs the most compact storage and improves the charge storage density of the electrode material.
In accordance with an embodiment of the present invention, the solute includes hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, trifluoromethanesulfonic acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ammonia water, lithium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, lithium nitrate, sodium nitrate, potassium nitrate, zinc nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate, lithium phosphate, sodium phosphate, potassium phosphate, zinc phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, lithium perchlorate, sodium perchlorate, potassium perchlorate, zinc perchlorate, magnesium perchlorate, calcium perchlorate, aluminum perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, zinc tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, aluminum tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate at least one of potassium hexafluorophosphate, zinc hexafluorophosphate, magnesium hexafluorophosphate, calcium hexafluorophosphate, aluminum hexafluorophosphate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, lithium trifluoromethanesulfonyl imide, sodium trifluoromethanesulfonyl imide, potassium trifluoromethanesulfonyl imide, zinc trifluoromethanesulfonyl imide, magnesium trifluoromethanesulfonyl imide, calcium trifluoromethanesulfonyl imide, aluminum trifluoromethanesulfonyl imide, lithium chloride, sodium chloride, potassium chloride, zinc chloride, magnesium chloride, calcium chloride, aluminum chloride, lithium bromide, sodium bromide, potassium bromide, zinc bromide, magnesium bromide, calcium bromide, aluminum bromide, lithium iodide, sodium iodide, potassium iodide, zinc iodide, magnesium iodide, calcium iodide, and aluminum iodide. Therefore, the self-adaptive remodeling of the characteristic holes is more beneficial to the electrode material to continuously adapt to the ion storage requirement, and the prop ions have good electrochemical stability in the working potential range.
According to an embodiment of the present invention, the solvent includes at least one of water, acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and 1, 3-dioxolane. Therefore, the prepared electrolyte has good electrochemical stability and higher ionic conductivity.
According to an embodiment of the present invention, the concentration of the active electrolyte is 0.01 to 10mol/L. Therefore, the prepared electrolyte has good electrochemical stability and higher ionic conductivity.
According to an embodiment of the present invention, the counter electrode includes a platinum sheet electrode, a platinum wire electrode, an activated carbon electrode, a graphite rod electrode, or a graphite paper electrode. Therefore, the three-electrode electrochemical system is favorable for obtaining stable voltage, and the stability of the active electrolyte when pillar ions are embedded into and separated from the characteristic holes is further improved.
According to an embodiment of the invention, the reference electrode comprises a silver-silver chloride electrode, a saturated calomel electrode, a mercury-oxidized mercury electrode, a mercury-mercurous sulfate electrode, a silver wire electrode or a standard hydrogen electrode. Therefore, the three-electrode electrochemical system is more favorable for obtaining stable voltage, and further, the stability of the active electrolyte when pillar ions are embedded into and separated from the characteristic holes is improved.
According to an embodiment of the present invention, the potential interval is a potential interval between reductive decomposition and oxidative decomposition of the electrolyte. The electrochemical scanning speed is 0.01-100 mV/s. Therefore, under the drive of an electric field, the effect of embedding ions serving as struts into the characteristic holes of the working electrode is better, so that the self-adaptive remodeling of the hole structure of the electrode material is more facilitated.
According to an embodiment of the present invention, the method for remolding the pore structure of the adaptive electrode material further comprises: and (3) cleaning the electrode material obtained in the step (3). Thus, the electrolyte and remaining impurities on the surface of the electrode material can be effectively removed.
In another aspect of the invention, an electrode material is provided. According to an embodiment of the invention, the electrodeThe material is prepared by the method. Thus, the remolded pore structure in the electrode material can effectively contain solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the electrode material shows the ultrahigh charge storage density, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the traditional capacitance material is solved.
In yet another aspect, the present invention provides an energy storage device. According to an embodiment of the invention, the energy storage device comprises the electrode material described previously. Therefore, the energy storage device has the advantages of high specific capacity, good multiplying power performance, high energy density, strong stability, good circularity and the like.
According to an embodiment of the invention, the energy storage device comprises an aluminum ion capacitor, an aqueous supercapacitor, an organic supercapacitor, an ionic liquid supercapacitor, a metal ion hybrid supercapacitor or a secondary battery. Therefore, the electrode material can be widely applied to various energy storage devices, and has strong practicability and high application value.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a flow chart of a method for reshaping an electrode material pore structure in accordance with one embodiment of the present invention.
FIG. 2 is a schematic representation of the pore structure of a remolded electrode material in accordance with one embodiment of the present invention.
FIG. 3 is a flow chart of a method for reshaping an electrode material pore structure in accordance with yet another embodiment of the present invention.
Fig. 4 is a nitrogen adsorption and desorption curve of the graphene electrode material of example 1 of the present invention.
Fig. 5 is a pore size distribution curve of the graphene electrode material of example 1 of the present invention.
FIG. 6 shows the structure of the graphene electrode of example 1 before the pore structure of the graphene electrode is remodeled 2 (SO 4 ) 3 Cyclic voltammogram in the electrolyte.
FIG. 7 is a graph of the graphene electrode of example 1 of the present invention at H 2 SO 4 Cyclic voltammograms at pore structure remodeling in the electrolyte.
FIG. 8 is a graph showing the pore structure of the graphene electrode of example 1 of the present invention at H 2 SO 4 After electrolyte remodeling, at Al 2 (SO 4 ) 3 Cyclic voltammogram in the electrolyte.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for adaptively remolding the pore structure of an electrode material. According to an embodiment of the invention, referring to fig. 1, the method comprises:
s100: mixing nano active material, conductive agent, binder and dispersing agent
In the step, firstly, the nano active material is fully ground to obtain uniform powder, and then the uniform powder is mixed with the conductive agent, the binder and the dispersing agent to obtain the electrode slurry.
According to embodiments of the present invention, the nano-active material may include, but is not limited to, graphene, graphite alkyne, molybdenum disulfide, hexagonal boron nitride, graphite phase C 3 N 4 At least one of black phosphazene, silylene oxide, two-dimensional transition metal carbonitride MXenes. Therefore, on one hand, the method has good universality, can realize the pore structure remodeling of various nano active materials, and further provides a rich material system for the construction of high-performance energy storage devices; on the other hand, the nano active material composed of the above materials has compact and ordered microstructure andthe electrode material has high specific capacity. In addition, the form of the above-mentioned nano-active material is not particularly limited, and one skilled in the art may select according to practical situations, for example, the form of the nano-active material may include at least one of solid powder, one-dimensional fiber, two-dimensional film, three-dimensional foam, and bulk material.
According to the embodiment of the invention, the mixing ratio of the nano active material, the conductive agent and the binder is not particularly limited, and a person skilled in the art can adjust the addition amount of the conductive agent and the binder according to the conductivity of the nano active material, so that the prepared electrode material has better electrochemical performance, and preferably, the mass ratio of the nano active material, the conductive agent and the binder can be 8:1:1, the electrode material prepared by adopting the formula has a compact and ordered microstructure and higher energy storage property, so that the specific capacity of the prepared electrode material can be effectively improved.
According to the embodiment of the invention, the type of the conductive agent material is not particularly limited, and a person skilled in the art can flexibly select the conductive agent according to actual needs, for example, the conductive agent can include at least one of conductive carbon black, acetylene black, ketjen black, single-layer graphene nano sheets, single-wall carbon nano tubes, multi-wall carbon nano tubes and graphite powder, so that the conductive agent not only has better chemical corrosion resistance, but also can enable the prepared electrode material to have better conductivity.
According to the embodiment of the present invention, the type of the binder material is not particularly limited, and one skilled in the art may flexibly select according to actual needs, for example, the binder may include, but is not limited to, at least one of polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyethylene oxide, and sodium alginate, whereby mechanical stability of the prepared electrode material may be further improved, and charge storage density of the electrode material may be further advantageously improved.
According to the embodiment of the present invention, the type of the dispersant material is not particularly limited, and a person skilled in the art can flexibly select according to actual needs, for example, the dispersant may include, but is not limited to, at least one of water, ethanol, ethylene glycol, acetone, acetonitrile, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide and dimethylsulfoxide, thereby achieving both high-efficiency, low-cost dissolution and dispersion effects.
S200: electrode paste is loaded on the surface of current collector
In this step, the electrode paste obtained in the above step S100 is loaded on the surface of the current collector, and the electrode paste is loaded on both the upper and lower surfaces of the current collector, and then dried, and finally cut to obtain an electrode.
According to the embodiment of the present invention, the type of the current collector is not particularly limited, and a person skilled in the art may flexibly select according to actual needs, for example, the current collector may include, but is not limited to, at least one of copper foil, aluminum foil, titanium foil, nickel foil, graphite foil, gold sheet, platinum sheet, stainless steel strip, stainless steel mesh, foam nickel, foam copper, carbon cloth and carbon paper, thereby facilitating the preparation of an electrode, and may enable the prepared electrode to have lower quality and better mechanical properties.
According to the embodiment of the invention, the loading mode of the electrode slurry is not particularly limited, and a person skilled in the art can flexibly select the electrode slurry according to actual needs, for example, not only a traditional coating method but also a method such as vacuum filtration, electrostatic spinning, wet spinning, interface assembly and the like can be adopted to prepare a self-supporting electrode, so that the electrode preparation method has a mature process route, has good compatibility with various electrode materials and production processes, and is easy for large-scale production.
S300: the prepared electrode is used as a working electrode, a counter electrode and a reference electrode are connected, a three-electrode electrochemical system is assembled in an active electrolyte, and electrochemical scanning is carried out in a certain potential interval
In this step, the electrode obtained in the above step S200 is used as a working electrode, and a counter electrode and a reference electrode are connected, and a three-electrode electrochemical system is assembled in an active electrolyte and a certain electric current is applied theretoElectrochemical scanning is carried out in a bit zone, cations and/or anions in the active electrolyte serve as ions with a supporting column function under the driving of electric field force, and characteristic holes of the electrode material are circularly embedded and extracted, so that the electrode material is subjected to self-adaptive remodeling (refer to figure 2) while continuously adapting to ion storage requirements, and the remolded hole structure in the obtained electrode material can effectively contain large-size solvated Al 3+ 、Mg 2+ 、Ca 2 + Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the charge storage density of the electrode material is effectively improved, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the electrode material in the prior art is solved; meanwhile, the remolding method has good universality, can realize the remolding of the pore structure of various nano active materials, further provides a rich material system for the construction of high-performance energy storage devices, and has important scientific value and practical significance for further developing the high-performance energy storage devices.
According to the embodiment of the invention, a three-electrode electrochemical system can be subjected to electrochemical scanning in a certain potential interval by adopting an electrochemical technology, wherein the electrochemical technology can comprise a cyclic voltammetry, and can also adopt a constant current charge-discharge method, a constant voltage charge-discharge method, a square wave current method, a square wave potential method, a pulse wave current method, a pulse wave potential method and the like according to actual requirements. In addition, the pore structure of the electrode material is preferably remolded by adopting a cyclic voltammetry, preferably, the potential interval can be a potential interval between reductive decomposition and oxidative decomposition of the electrolyte, the scanning speed can be 0.01-100 mV/s, and particularly can be 0.01mV/s, 0.05mV/s, 0.1mV/s, 0.5mV/s, 1mV/s, 5mV/s, 10mV/s, 20mV/s, 30mV/s, 40mV/s, 50mV/s, 70mV/s, 100mV/s and the like, so that the effect of embedding ions serving as support posts into characteristic pores of the working electrode under the driving of an electric field is better, and the self-adaptive remolding of the pore structure of the electrode material is more beneficial.
According to an embodiment of the invention, in this step, the active electrolyte comprises a solute and a solvent, wherein the solute comprises at least one anion or cation having a size between that of a solvated metal ion and the characteristic pores, such as metal ions including but not limited to Al 3+ 、Mg 2+ And Ca 2+ At least one of the anions or cations, due to the size of the anions or cations being only slightly larger than the size of the characteristic holes, allows the ions to be more easily embedded and extracted into the characteristic holes of the working electrode through partial desolvation, thereby being more beneficial to the electrode material to complete the self-adaptive remodeling of the characteristic holes while continuously adapting to the ion storage requirement, and the finally formed remodelling hole structure can accommodate solvated Al 3+ 、Mg 2+ And Ca 2+ The plasma can further enable the remolded pore structure in the electrode material to realize solvation of Al 3+ 、Mg 2+ And Ca 2+ The high-efficiency storage of the plasma effectively improves the charge storage density of the electrode material, so that the electrode material has ultrahigh specific capacity, and further the solvation of the electrode material in Al is obviously improved 3+ 、Mg 2+ And Ca 2+ Electrochemical performance in plasma electrolytes.
In accordance with an embodiment of the present invention, the solute may include, but is not limited to, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, trifluoromethanesulfonic acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, aqueous ammonia, lithium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, lithium nitrate, sodium nitrate, potassium nitrate, zinc nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate, lithium phosphate, sodium phosphate, potassium phosphate, zinc phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, lithium perchlorate, sodium perchlorate, potassium perchlorate, zinc perchlorate, magnesium perchlorate, calcium perchlorate, aluminum perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, zinc tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, aluminum tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate at least one of potassium hexafluorophosphate, zinc hexafluorophosphate, magnesium hexafluorophosphate, calcium hexafluorophosphate, aluminum hexafluorophosphate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, lithium trifluoromethanesulfonyl imide, sodium trifluoromethanesulfonyl imide, potassium trifluoromethanesulfonyl imide, zinc trifluoromethanesulfonyl imide, magnesium trifluoromethanesulfonyl imide, calcium trifluoromethanesulfonyl imide, aluminum trifluoromethanesulfonyl imide, lithium chloride, sodium chloride, potassium chloride, zinc chloride, magnesium chloride, calcium chloride, aluminum chloride, lithium bromide, sodium bromide, potassium bromide, zinc bromide, magnesium bromide, calcium bromide, aluminum bromide, lithium iodide, sodium iodide, potassium iodide, zinc iodide, magnesium iodide, calcium iodide, and aluminum iodide. Therefore, the solute composed of the materials can provide the pillar ions with supporting effect (it is understood that the pillar ions are anions or cations with the size between that of solvated ions and characteristic holes of the materials in the solute), so that the electrode material can be more beneficial to completing self-adaptive remodeling of the characteristic holes while continuously adapting to the ion storage requirements, and the pillar ions have good electrochemical stability in the working potential range.
According to an embodiment of the present invention, the solvent may include, but is not limited to, at least one of water, acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and 1, 3-dioxolane. Therefore, the prepared electrolyte has good electrochemical stability and higher ionic conductivity.
According to the embodiment of the invention, the concentration of the active electrolyte can be 0.01-10 mol/L, specifically 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 3mol/L, 5mol/L, 7mol/L, 10mol/L and the like, and the inventor discovers that the concentration of the electrolyte is controlled to be 0.01-10 mol/L, so that the prepared electrolyte has good electrochemical stability and higher ionic conductivity.
According to embodiments of the present invention, the counter electrode may include, but is not limited to, a platinum sheet electrode, a platinum wire electrode, an activated carbon electrode, a graphite rod electrode, or a graphite paper electrode. Therefore, the three-electrode electrochemical system is favorable for obtaining stable voltage, and the stability of the active electrolyte when pillar ions are embedded into and separated from the characteristic holes is further improved.
According to embodiments of the present invention, the reference electrode may include, but is not limited to, a silver-silver chloride electrode, a saturated calomel electrode, a mercury-oxidized mercury electrode, a mercury-mercurous sulfate electrode, a silver wire electrode, or a standard hydrogen electrode. Therefore, the three-electrode electrochemical system is more favorable for obtaining stable voltage, and further, the stability of the active electrolyte when pillar ions are embedded into and separated from the characteristic holes is improved.
The inventor finds that by loading an electrode slurry comprising a nano active material, a conductive agent, a binder and a dispersing agent on the surface of a current collector to obtain an electrode serving as a working electrode, connecting a counter electrode and a reference electrode, assembling a three-electrode electrochemical system in an active electrolyte and performing electrochemical scanning in a certain potential interval, and circularly embedding and extracting cations and/or anions in the active electrolyte to serve as ions with a supporting role into and out of characteristic holes of the electrode material under the driving of electric field force, the electrode material is enabled to continuously adapt to the ion storage requirement and simultaneously complete self-adaptive remodeling of the characteristic holes, so that the remolded hole structure in the obtained electrode material can effectively contain solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the charge storage density of the electrode material is effectively improved, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the electrode material in the prior art is solved; meanwhile, the remolding method has good universality, can realize the remolding of the pore structure of various nano active materials, further provides a rich material system for the construction of high-performance energy storage devices, and has important scientific value and practical significance for further developing the high-performance energy storage devices; in addition, the electrode preparation method in the method has mature process route, good compatibility with various electrode materials and production processes, and the electrochemical self-adaptive pore structure remodeling process and production process used in the methodThe related technologies in the electroplating and electrolysis industry have good compatibility, the remodeling process of the characteristic pore structure of the electrode material can be completed by adopting the production process of the electroplating and electrolysis industry, the cost is low, and the large-scale production is easy. Therefore, the method is simple and convenient to operate, repeatable, low in cost and easy to realize and realize large-scale production, and the electrode material obtained by adopting the method has a pore structure capable of effectively accommodating large-size solvated Al 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is stored most densely, so that the electrode material exhibits an ultra-high charge storage density.
According to an embodiment of the present invention, referring to fig. 3, the above-mentioned method for remolding an adaptive electrode material pore structure further includes:
s400: cleaning the electrode material obtained in the step S300
In this step, the electrode material obtained in step S300 is cleaned, and the electrolyte and the remaining impurities on the surface of the electrode material are effectively removed.
According to the embodiment of the invention, the method for cleaning the electrode material is not particularly limited, and a person skilled in the art can select the method according to the actual situation as long as the remodeled electrode material pore structure is not damaged, for example, the method for cleaning the electrode material can adopt a dialysis method, a room temperature extraction method, a supercritical fluid extraction method, a suction filtration washing method and the like, so that the cleaning effect of the electrode material is better, the stability of the remodeled electrode material pore structure is better, preferably, the remodeled electrode material with the pore structure is dialyzed by adopting a dialysis method, the dialysis process is preferably carried out at room temperature for not less than 12 hours, and at least water is changed for 3 times in the dialysis process, so that the electrode material obtained in the step is fully soaked and dialyzed in a cleaning solvent until the ion conductivity of dialysate is reduced to 20 mu S/cm, and then the electrode material is taken out for standby. Preferably, the cleaning solvent used for soaking dialysis can be the same as the solvent used for preparing the electrolyte, so that the situation that the remolded pore structure in the electrode material collapses due to replacement of the cleaning solvent can be effectively avoided.
Further, compared with the prior art, the self-adaptive electrode material pore structure remodeling method has at least the following beneficial effects:
first, the electrode preparation method used in the method has mature process route, good compatibility with various electrode materials and the existing electrode production line, suitability for mass production and preparation and low cost.
Secondly, the electrochemical self-adaptive pore structure remodeling process used in the method has good compatibility with the existing electroplating and electrolysis industrial production line, can finish the remodeling of the pore structure of the electrode material along the existing electroplating and electrolysis industrial production line, and has good mass production and preparation prospects.
Thirdly, the electrode material prepared by the self-adaptive electrode material pore structure remolding method has a pore structure which can effectively accommodate large-size solvated Al 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the electrode material shows the ultrahigh charge storage density, and the problem that the charge storage capacity is too low due to too large or too small characteristic holes of the traditional capacitance type material is solved.
Fourth, the method for remolding the pore structure of the self-adaptive electrode material disclosed by the invention has good universality, can realize remolding of the pore structure of various nano-active materials including graphene and two-dimensional transition metal carbonitrides (MXenes), further provides a rich material system for constructing a high-performance capacitor, and has important scientific value and practical significance for developing a future high-performance capacitive electrochemical energy storage device.
In another aspect of the invention, an electrode material is provided. According to an embodiment of the invention, the electrode material is prepared by the method described above. Thus, the remolded pore structure in the electrode material can effectively contain solvated Al with large size 3+ 、Mg 2+ 、Ca 2+ Plasma, at the same time can solvate Al 3+ 、Mg 2+ 、Ca 2+ The plasma is used for carrying out the most compact storage, so that the electrode material shows the ultrahigh charge storage density, and the problem of low charge storage capacity caused by overlarge or undersize characteristic holes in the traditional capacitance material is solved. It should be noted that the technical features and effects described in the above-mentioned method for remolding the pore structure of the adaptive electrode material are also applicable to the electrode material, and are not described in detail herein.
In yet another aspect, the present invention provides an energy storage device. According to the embodiment of the invention, the energy storage device comprises the electrode material, so that the energy storage device has the advantages of high specific capacity, good rate capability, high energy density, strong stability, good circularity and the like.
According to the embodiment of the invention, the energy storage device can comprise an aluminum ion capacitor, a water system super capacitor, an organic super capacitor, an ionic liquid super capacitor, a metal ion hybrid super capacitor or a secondary battery, so that the electrode material can be widely applied to various energy storage devices, and has strong practicability and high application value.
It should be noted that the technical features and effects described with respect to the electrode material are also applicable to the energy storage device, and are not described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
The graphene oxide dispersions referred to in the following examples were prepared by Hummers method, and the specific preparation method is as follows: 200mL of concentrated sulfuric acid (98 wt%), 8g of natural crystalline flake graphite (325 mesh) and 4g of sodium nitrate were sequentially added to a beaker, after which the beaker was fixed in an ice-water bath and mechanically stirred; after stirring for 30min, slowly adding 32g of potassium permanganate into the mixture, and continuing to react in the ice water bath for 2h; transferring the beaker into a constant-temperature water bath at 35 ℃ and stirring for 30min, and slowly adding 300mL of deionized water into the beaker, wherein the water adding process ensures that the temperature of a reaction system is not more than 40 ℃; transferring the beaker into a constant-temperature water bath at 98 ℃ for about 40 minutes to turn the system into bright yellow, and stopping the reaction at the moment; placing the beaker in a fume hood, adding 900mL of warm water for dilution, then adding 40mL of hydrogen peroxide, stirring uniformly, and filtering while hot to form a filter cake; washing the filter cake with 5wt% hydrochloric acid for three times, and carrying out suction filtration washing on the filter cake for multiple times with distilled water; and then, re-dispersing the filter cake in deionized water, filling the deionized water into a dialysis bag for dialysis, and transferring the graphene oxide dispersion liquid into a reagent bottle for standby after the electric conductivity of the dialysate is reduced to 20 mu S/cm.
Ti involved in the following examples 3 C 2 T x The MXene dispersion liquid is prepared by adopting an improved hydrofluoric acid etching method, and the specific preparation process is as follows: sequentially adding 40mL of concentrated hydrochloric acid (9 mol/L) and 2g of lithium fluoride into a polytetrafluoroethylene container, starting magnetic stirring, and slowly adding 2g of titanium aluminum carbide ceramic powder (400 meshes); after 36h of reaction at 25 ℃, 100mL of deionized water was added to the polytetrafluoroethylene vessel to terminate the reaction; repeatedly centrifugally washing the obtained product until the pH value of the supernatant is close to 7; redispersing the washed product in 100mL deionized water, performing water bath ultrasonic treatment under the protection of argon for 20min to fully strip the product, and performing centrifugal impurity removal to obtain Ti 3 C 2 T x And (3) a dispersion.
The characterization and testing methods involved in the following examples are as follows:
(1) Nitrogen adsorption and desorption instrument: the specific surface area and pore size distribution of the electrode material were tested.
(2) Electrochemical workstation: and carrying out self-adaptive electrochemical remodeling on the electrode material pore structure, and testing the electrochemical performance of the electrode material pore structure before and after remodeling.
Example 1
(1) Preparing 3mg/mL graphene oxide dispersion liquid by using the Hummers method, adding 0.1mol/L potassium hydroxide into the graphene oxide dispersion liquid, adopting a one-step hydrothermal method to reduce the graphene dispersion liquid to obtain graphene hydrogel, washing and drying the graphene hydrogel to obtain a graphene block material, fully grinding the graphene block material to obtain uniform active material powder, and mixing the graphene block material powder, conductive carbon black and polyvinylidene fluoride according to a mass ratio of 8:1: and 1, mixing materials, dispersing the materials in N-methyl pyrrolidone (NMP) to obtain electrode slurry, uniformly coating the electrode slurry on titanium foil, drying in a vacuum oven, and cutting to obtain the graphene electrode.
(2) Preparing sulfuric acid electrolyte with the concentration of 0.1mol/L, wherein sulfuric acid is selected as electrolyte, deionized water is selected as solvent, and SO is adopted in the electrolyte 4 2- Pillar ions that remodel the pore structure.
(3) The prepared graphene electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a silver-silver chloride electrode is used as a reference electrode, and a three-electrode electrochemical system is assembled in sulfuric acid electrolyte with the concentration of 0.1 mol/L. Scanning 50 circles by cyclic voltammetry at a scanning speed of 20mV/s in a potential range of-0.2-1.0V by using SO at high potential 4 2- The characteristic holes of the electrode material are continuously embedded and separated to realize the remodeling of the hole structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode material for later use.
Conclusion: fig. 4 is a nitrogen adsorption and desorption curve of the graphene electrode material of example 1. Fig. 5 is a pore size distribution curve of the graphene electrode material of example 1. FIG. 6 is a graph showing the structure of the graphene electrode of example 1 before the pore structure is remodelled with Al 2 (SO 4 ) 3 Cyclic voltammogram in the electrolyte. Fig. 7 is a graph of graphene electrode at H of example 1 2 SO 4 Cyclic voltammograms at pore structure remodeling in the electrolyte. FIG. 8 is a graph of graphene electrode at H of example 1 2 SO 4 After electrolyte remodeling, at Al 2 (SO 4 ) 3 Cyclic voltammogram in the electrolyte. As shown in fig. 4, the graphene electrode material prepared by the method of this example had 515m 2 The high specific surface area per gram and its nitrogen adsorption and desorption curve (fig. 4) also show that both micropores and mesopores are present in the graphene electrode. As shown in FIG. 5, the characteristic pore size is 0.68nm, which is far smaller than solvated Al, by fitting the pore structure of the graphene electrode by the density functional theory 3+ Diameter (0.95 nm), thus analyzing solvated Al from a steric hindrance point of view 3+ Cannot be on the stoneThe graphene electrode material is effectively stored in the characteristic holes. As can be seen from the cyclic voltammogram shown in FIG. 6, in solvated Al 3+ The capacity of the graphene electrode is limited in a low potential region contributing to capacity, and the fact that the pore structure of the electrode material cannot effectively accommodate solvated Al is proved 3+ . Placing the graphene electrode into a solution containing SO 4 2- Electrochemical activation scans were performed in sulfuric acid electrolyte to remodel its pore structure. As shown in FIG. 7, the response current of the cyclic voltammogram increases continuously during the pore structure remodeling process, indicating that at H 2 SO 4 SO in electrolyte 4 2- Under the action of electric field force, the material continuously enters the characteristic holes of the electrode material and gradually expands the characteristic holes, and after repeated charge and discharge scanning, the response current of the cyclic voltammogram gradually tends to be balanced, which indicates that the remodeling of the hole structure reaches a steady state. As shown in FIG. 8, will pass through H 2 SO 4 Electrode material with remodelling electrolyte pore structure is restored to contain solvated Al 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process, passing through SO 4 2- The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene electrode material before pore structure remodeling is only 389C/cm 3 And the specific capacity of the porous structure is improved to 660C/cm after the pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 2
(1) Preparing graphene oxide dispersion liquid with the concentration of 5mg/mL by using the Hummers method, reducing by adopting a one-step hydrothermal method to obtain graphene hydrogel, directly drying to obtain a graphene block material, fully grinding the graphene block material to obtain a uniform active material, and mixing the uniform active material with acetylene black and Polytetrafluoroethylene (PTFE) according to a mass ratio of 9:0.5: and 0.5, mixing materials, dispersing the materials in ethanol to obtain electrode slurry, rolling the electrode slurry into a film, loading the film on a stainless steel net, drying in a blast oven, and cutting to obtain the graphene electrode.
(2) Preparing 21mol/kg LiTFSI electrolyte, wherein bis (trifluoromethanesulfonyl imide) Lithium (LiTFSI) is selected as electrolyte, deionized water is selected as solvent, and TFSI is selected in the electrolyte - Pillar ions that remodel the pore structure.
(3) The prepared graphene electrode is used as a working electrode, an activated carbon electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a three-electrode electrochemical system is assembled in LiTFSI electrolyte of 21 mol/kg. Scanning 20 circles by cyclic voltammetry at a scanning speed of 5mV/s in a potential range of-0.9V, and using TFSI under high potential - Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode material for later use.
Conclusion: the graphene electrode material prepared by the method of this example had a particle size of 362m 2 Specific surface area per gram, characteristic pore size of 0.65nm, which is much smaller than solvated Al 3+ Diameter (0.95 nm), thus analyzing solvated Al from a steric hindrance point of view 3+ And cannot be effectively stored in the characteristic holes of the graphene electrode material. Re-incorporating solvated Al into an electrode material subjected to LiTFSI electrolyte pore structure remodeling 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process, passing through TFSI - The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene electrode material before pore structure remodeling is only 285C/cm 3 And the specific capacity of the pore structure is increased to 524C/cm after the pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 3
(1) Preparing graphene oxide dispersion liquid with the concentration of 0.1mg/mL by utilizing the Hummers method, adding hydrazine hydrate solution into the graphene oxide dispersion liquid, reacting the hydrazine hydrate solution with the graphene oxide dispersion liquid in a mass ratio of 1:1 in a 90-DEG blast oven for 2 hours, directly carrying out suction filtration on the obtained dispersion liquid to form a film, repeatedly cleaning and removing impurities by deionized water, drying in the 60-DEG blast oven, and stripping from the substrate to obtain the self-supporting graphene membrane electrode.
(2) Preparing phosphoric acid electrolyte with the concentration of 1mol/L, wherein phosphoric acid is selected as electrolyte, deionized water is selected as solvent, and PO is added into the electrolyte 4 3- Pillar ions that remodel the pore structure.
(3) The prepared graphene membrane electrode is used as a working electrode, a graphite rod electrode is used as a counter electrode, a mercury-mercurous sulfate electrode is used as a reference electrode, and a three-electrode electrochemical system is assembled in phosphoric acid electrolyte with the concentration of 1 mol/L. Scanning 10 circles by cyclic voltammetry at a scanning speed of 1mV/s in a potential range of-0.3-1.0V by using PO under high potential 4 3- Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode for later use.
Conclusion: the graphene membrane electrode prepared by the method of this example had a diameter of 158m 2 Specific surface area/g, characteristic interlayer spacing (i.e., characteristic pore size) of 0.58nm, which is much less than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ And cannot be effectively stored in the characteristic holes of the graphene electrode material. Re-incorporating solvated Al into electrode material subjected to pore structure remodeling of phosphoric acid electrolyte 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the pore-entry process of solvated ions is usually accompanied by partial desolvation process through PO 4 3- The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene electrode material before pore structure remodeling is only 136C/cm 3 And its specific capacity is raised to 408C/cm after the pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 4
(1) Preparing graphene oxide dispersion liquid with the concentration of 2mg/mL by using the Hummers method, adding 0.2mol/L potassium hydroxide into the graphene oxide dispersion liquid, adopting a one-step hydrothermal method to reduce the graphene oxide dispersion liquid to obtain graphene hydrogel, washing and drying the graphene hydrogel to obtain a graphene block material, fully grinding the graphene block material to obtain uniform active material powder, and mixing the graphene block material powder with ketjen black and sodium carboxymethyl cellulose (CMC) according to a mass ratio of 7:2: and 1, mixing materials, dispersing the materials in water to obtain electrode slurry, uniformly coating the electrode slurry on an aluminum foil, drying in a vacuum oven, and cutting to obtain the graphene electrode.
(2) Preparing LiPF of 2mol/L 6 An electrolyte solution in which lithium hexafluorophosphate (LiPF) 6 ) As an electrolyte, a mixed solution of dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) in a volume ratio of 1:1 is used as a solvent; PF in electrolyte 6 - Acting as a pillar ion for pore structure remodeling.
(3) The prepared graphene electrode is used as a working electrode, a metal lithium electrode is used as a counter electrode and a reference electrode, and 2mol/L LiPF is used 6 The electrolyte and the glass fiber separator are assembled into an electrochemical system of a button half cell. Charging and discharging for 10 circles in a potential range of 3.0-5.3V by constant current charging and discharging method at a current density of 0.2A/g, and using PF at high potential 6 - Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in dimethyl carbonate (DMC) until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode for later use.
Conclusion: the graphene electrode material prepared by the method of this example had a thickness of 586m 2 High specific surface area per gram, characteristic pore size of 0.75nm, which is less than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ And cannot be effectively stored in the characteristic holes of the graphene electrode material. Re-incorporating solvated Al into electrode material subjected to pore structure remodeling of lithium hexafluorophosphate electrolyte 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the solvation ion entry process is usually accompanied by partial desolvation process through the PF 6 - The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ By partial desolvation of the conditions of the pore, soCan solvate Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene electrode material before pore structure remodeling is only 372C/cm 3 And its specific capacity is raised to 766C/cm after pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 5
(1) Preparing graphene oxide slurry with the concentration of 35mg/mL by using the Hummers method, extruding the graphene oxide slurry into a coagulating bath of calcium chloride by adopting a wet spinning technology, and solidifying to obtain the graphene oxide fiber. Immersing the graphene oxide fiber into a hydroiodic acid solution for full reduction, immersing and washing in an ethanol solution, and airing at room temperature to obtain the self-supporting graphene fiber electrode.
(2) Preparing 9mol/L NaClO 4 +0.1mol/L HClO 4 Wherein, two substances of sodium perchlorate and perchloric acid are selected as electrolytes, deionized water is used as solvent; in the electrolyte, clO 4 - Acting as a pillar ion for pore structure remodeling.
(3) Self-supporting graphene fiber electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, a silver wire electrode is used as a reference electrode, and 9mol/L NaClO is used 4 +0.1mol/L HClO 4 The hybrid electrolyte and the cellulose paper separator are assembled into a fibrous three-electrode electrochemical system. The cyclic voltammetry is adopted to scan 10 circles at a scanning speed of 0.1mV/s in a potential range of-0.8 to 1.0V, and ClO under high potential is utilized 4 - Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the self-supporting graphene fiber electrode with the remodeled pore structure in deionized water until the ion conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode material for later use.
Conclusion: the self-supporting graphene fiber electrode prepared by the method of the embodiment has 273m 2 High specific surface area per gram, characteristic pore size of 0.68nm, which is less than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ And cannot be effectively stored in the characteristic holes of the graphene fibers. Will pass through NaClO 4 +HClO 4 Is re-incorporated into solvated Al-containing electrode materials with remodelling of the hybrid electrolyte pore structure 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process, passing through ClO 4 - The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene fiber electrode before pore structure remodeling is only 162C/cm 3 And its specific capacity is raised to 336C/cm after pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 6
(1) Preparing graphene oxide dispersion liquid with the concentration of 2mg/mL by using a Hummers method, reducing by using a one-step hydrothermal method to obtain graphene hydrogel, freeze-drying to obtain graphene three-dimensional foam, and cutting the graphene three-dimensional foam into wafers with the diameter of 1cm and the thickness of 1mm by using laser to obtain the graphene three-dimensional foam electrode.
(2) Preparing potassium hydroxide electrolyte with the concentration of 0.05mol/L, wherein potassium hydroxide is selected as electrolyte, and deionized water is selected as solvent; in the electrolyte, K + Acting as a pillar ion for pore structure remodeling.
(3) Graphene three-dimensional foam electrode as workerThe electrode, the active carbon electrode, the silver wire electrode and the potassium hydroxide electrolyte with the concentration of 0.05mol/L, the non-woven membrane and the gold plate current collector are assembled into a sandwich type three-electrode electrochemical system. Scanning 20 circles by cyclic voltammetry at a scanning speed of 2mV/s in a potential range of-1.0-0.2V by using K under low potential + Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode for later use.
Conclusion: the graphene three-dimensional foam electrode prepared by the method of this example had 385m 2 The graphene three-dimensional foam electrode has an open macroporous structure but has a characteristic pore size of 0.58nm, which is far smaller than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ And cannot be effectively stored in the characteristic holes of the graphene electrode material. The electrode material remodelled by the potassium hydroxide electrolyte pore structure is remodelled to contain solvated Al 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process, passing through K + The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the graphene three-dimensional foam electrode before pore structure remodeling is only 218C/cm 3 And its specific capacity is raised to 425C/cm after pore structure remodeling 3 The method shows that the pore structure remodeling process can effectively remodel the characteristic pores of the electrode material, so that the electrode material has ultrahigh specific volumeThe amount of the electrode material is obviously improved in solvation of Al 3+ Electrochemical performance in an electrolyte.
Example 7
(1) Preparing 8mg/mL Ti by using the improved hydrofluoric acid etching method 3 C 2 T x MXene dispersion, 10mg/mL graphene oxide dispersion was prepared by the Hummers method, and Ti was used as a solvent 3 C 2 T x The volume ratio of the MXene dispersion liquid to the graphene oxide dispersion liquid is 4:1, the MXene dispersion liquid and the graphene oxide dispersion liquid are mixed and fully and ultrasonically dispersed uniformly, and then hydrothermal reduction assembly is carried out in a 120-DEG blast oven, wherein the reaction time is 24 hours. Directly drying the composite hydrogel to obtain a composite block material, and fully grinding the composite block material to obtain uniform active material powder; mixing the active material powder, high-crystalline graphite powder and Sodium Alginate (SA) according to the mass ratio of 8:1:1, dispersing the mixture in water to obtain electrode slurry, uniformly coating the electrode slurry on graphite foil, drying in a vacuum oven, and cutting to obtain the composite electrode.
(2) Preparing 1mol/L magnesium nitrate electrolyte, wherein magnesium nitrate is selected as electrolyte, deionized water is selected as solvent, and Mg in the electrolyte 2+ Acting as a pillar ion for pore structure remodeling.
(3) The prepared composite electrode is used as a working electrode, an active carbon electrode is used as a counter electrode, a silver-silver chloride electrode is used as a reference electrode, and a three-electrode electrochemical system is assembled in a magnesium nitrate electrolyte with the concentration of 1 mol/L. Activating electrode material with constant voltage charge-discharge method under-0.9V voltage, and reducing response current to 1×10 -6 A is less than or equal to A. The process uses Mg at low potential 2+ Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode for later use.
Conclusion: the composite electrode material prepared by the method of this example had 315m 2 High specific surface area per gram, characteristic pore size of 0.72nm, which is much smaller than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ And cannot be effectively stored in the characteristic holes of the composite electrode material. Re-incorporating solvated Al into the electrode material subjected to pore structure remodeling of magnesium nitrate electrolyte 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process through Mg 2+ The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Through testing, the specific capacity of the composite electrode material before pore structure remodeling is only 486C/cm 3 And its specific capacity is increased to 828C/cm after pore structure is remodeled 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
Example 8
(1) Preparing 2mg/mL Ti by using the improved hydrofluoric acid etching method 3 C 2 T x MXene dispersion, adding 1mol/L potassium hydroxide solution with equal volume, stirring under nitrogen protection for 20min, repeatedly centrifuging and washing the obtained suspension, vacuum filtering to obtain Ti 3 C 2 T x The MXene film is peeled from the substrate after being dried at room temperature to obtain self-supporting Ti 3 C 2 T x MXene membrane electrode.
(2) Preparing 10mol/L zinc chloride electrolyte, wherein zinc chloride is selected as electrolyte, deionized water is selected as solvent, and Zn in the electrolyte 2+ Acting as a pillar ion for pore structure remodeling.
(3) The prepared membrane electrode is used as a working electrode, a graphite paper electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and a three-electrode electrochemical system is assembled in 10mol/L zinc chloride electrolyte. Scanning 100 circles by cyclic voltammetry at a scanning speed of 20mV/s in a potential range of-1.0-0.2V, and utilizing Zn under low potential 2+ Is used for realizing the remodelling of the pore structure of the electrode material.
(4) And fully soaking and dialyzing the electrode material with the remodeled pore structure in deionized water until the ionic conductivity of the dialysate is reduced to 20 mu S/cm, and taking out the electrode for later use.
Conclusion: ti prepared by the method of this example 3 C 2 T x The specific surface area of the MXene membrane electrode is 78m 2 Although the specific surface area is small, the composition has rich interlayer structure and can be solvated Al 3+ Efficient storage provides potential active sites. In addition, ti 3 C 2 T x The characteristic interlayer spacing (i.e., characteristic pore size) of the MXene membrane electrode is 0.75nm, a value much smaller than solvated Al 3+ The diameter (0.95 nm) of (C) and therefore, from the perspective of steric hindrance, it is known that Al is solvated 3+ Cannot be made of the Ti 3 C 2 T x And the characteristic holes of the MXene membrane electrode are effectively stored. Re-incorporating solvated Al into electrode material subjected to zinc chloride electrolyte pore structure remodeling 3+ It was found by examination in the electrolyte of (2) that a pair of solvated Al appeared on the cyclic voltammogram 3+ Redox peaks embedded/extracted inside the characteristic pores of the material, indicating that the electrochemically remodeled characteristic pores are capable of solvating Al 3+ Efficient reversible storage is performed. This is mainly because the hole-entering process of solvated ions is usually accompanied by partial desolvation process, passing through Zn 2+ The remolded material features pores are still smaller than solvated Al 3+ But has satisfied the solvation of Al 3+ The conditions of partial desolvation mode pore entry can be used for solvating Al after repeated charge and discharge activation 3+ Efficient reversible storage is performed. Tested by the Ti 3 C 2 T x Ratio of MXene Membrane electrode before pore Structure remodelingThe capacity is 518C/cm 3 And its specific capacity is raised to 965C/cm after pore structure remodeling 3 The method shows that the pore structure remodeling process can effectively remodel characteristic pores of the electrode material, so that the electrode material has ultrahigh specific capacity, and further, the solvation of the electrode material in Al is obviously improved 3+ Electrochemical performance in an electrolyte.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.

Claims (10)

1. A method for adaptively remolding a pore structure of an electrode material, comprising:
(1) Mixing a nano active material, a conductive agent, a binder and a dispersing agent to obtain an electrode slurry;
(2) Loading the electrode slurry on the surface of a current collector so as to obtain an electrode;
(3) The electrode is used as a working electrode and is connected with a counter electrode and a reference electrode, a three-electrode electrochemical system is assembled in an active electrolyte, electrochemical scanning is carried out in a certain potential interval, and the living body is driven by an electric fieldCations and/or anions in the aqueous electrolyte intercalate into and deintercalate from the characteristic pores of the working electrode to remodel the pore structure of the electrode material; in step (3), the active electrolyte comprises a solute and a solvent, wherein the solute comprises at least one anion or cation having a size between that of a solvated metal ion and the characteristic pores, wherein the solvated metal ion comprises Al 3+ 、Mg 2+ And Ca 2+ At least one of them.
2. The method of claim 1, wherein in step (1), the nano-active material comprises graphene, graphite alkyne, molybdenum disulfide, hexagonal boron nitride, graphite phase C 3 N 4 At least one of black phosphazene, silylene oxide, two-dimensional transition metal carbonitride;
in step (1), the conductive agent comprises at least one of conductive carbon black, acetylene black, ketjen black, single-layer graphene nanoplatelets, single-walled carbon nanotubes, multi-walled carbon nanotubes, and graphite powder;
in the step (1), the binder comprises at least one of polytetrafluoroethylene, polyvinylidene fluoride, styrene-butadiene rubber, sodium carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyethylene oxide and sodium alginate;
in step (1), the dispersant includes at least one of water, ethanol, ethylene glycol, acetone, acetonitrile, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide, and dimethylsulfoxide.
3. The method of claim 1 or 2, wherein in step (2), the current collector comprises at least one of copper foil, aluminum foil, titanium foil, nickel foil, graphite foil, gold sheet, platinum sheet, stainless steel strip, stainless steel mesh, nickel foam, copper foam, carbon cloth, and carbon paper.
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the solute includes hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid, perchloric acid, trifluoromethanesulfonic acid, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, ammonia water, lithium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, lithium nitrate, sodium nitrate, potassium nitrate, zinc nitrate, magnesium nitrate, calcium nitrate, aluminum nitrate, lithium phosphate, sodium phosphate, potassium phosphate, zinc phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, lithium perchlorate, sodium perchlorate, potassium perchlorate, zinc perchlorate, magnesium perchlorate, calcium perchlorate, aluminum perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, zinc tetrafluoroborate, magnesium tetrafluoroborate, calcium tetrafluoroborate, aluminum tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate at least one of potassium hexafluorophosphate, zinc hexafluorophosphate, magnesium hexafluorophosphate, calcium hexafluorophosphate, aluminum hexafluorophosphate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, aluminum trifluoromethanesulfonate, lithium trifluoromethanesulfonyl imide, sodium trifluoromethanesulfonyl imide, potassium trifluoromethanesulfonyl imide, zinc trifluoromethanesulfonyl imide, magnesium trifluoromethanesulfonyl imide, calcium trifluoromethanesulfonyl imide, aluminum trifluoromethanesulfonyl imide, lithium chloride, sodium chloride, potassium chloride, zinc chloride, magnesium chloride, calcium chloride, aluminum chloride, lithium bromide, sodium bromide, potassium bromide, zinc bromide, magnesium bromide, calcium bromide, aluminum bromide, lithium iodide, sodium iodide, potassium iodide, zinc iodide, magnesium iodide, calcium iodide, and aluminum iodide;
The solvent comprises at least one of water, acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and 1, 3-dioxolane;
the concentration of the active electrolyte is 0.01-10 mol/L.
5. The method of claim 1 or 4, wherein the counter electrode comprises a platinum sheet electrode, a platinum wire electrode, an activated carbon electrode, a graphite rod electrode, or a graphite paper electrode;
the reference electrode comprises a silver-silver chloride electrode, a saturated calomel electrode, a mercury-mercury oxide electrode, a mercury-mercurous sulfate electrode, a silver wire electrode or a standard hydrogen electrode.
6. The method of claim 1, wherein the potential interval is a potential interval between reductive decomposition and oxidative decomposition of the electrolyte;
the electrochemical scanning speed is 0.01-100 mV/s.
7. The method as recited in claim 1, further comprising: and (3) cleaning the electrode material obtained in the step (3).
8. An electrode material, characterized in that it is prepared by the method according to any one of claims 1 to 7.
9. An energy storage device comprising the electrode material of claim 8.
10. The energy storage device of claim 9, wherein the energy storage device comprises an aluminum ion capacitor, an aqueous supercapacitor, an organic supercapacitor, an ionic liquid supercapacitor, a metal ion hybrid supercapacitor, or a secondary battery.
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