CN116313559A - Metal oxide based capacitive ion diode and preparation method and application thereof - Google Patents
Metal oxide based capacitive ion diode and preparation method and application thereof Download PDFInfo
- Publication number
- CN116313559A CN116313559A CN202310217053.8A CN202310217053A CN116313559A CN 116313559 A CN116313559 A CN 116313559A CN 202310217053 A CN202310217053 A CN 202310217053A CN 116313559 A CN116313559 A CN 116313559A
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- Prior art keywords
- metal oxide
- electrolyte
- electrode
- porous carbon
- ion diode
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 105
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 127
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003792 electrolyte Substances 0.000 claims abstract description 93
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
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- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001450 anions Chemical class 0.000 claims abstract description 25
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- 238000009830 intercalation Methods 0.000 claims abstract description 8
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 77
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 66
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Images
Classifications
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
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Abstract
The invention discloses a metal oxide based capacitance type ion diode and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a metal oxide based working electrode and a porous carbon based counter electrode, wherein the metal oxide based working electrode uses metal oxide with intercalation pseudocapacitance behavior; preparing electrolyte, wherein only one ion in anions and cations of the electrolyte can be stored in metal oxide; and assembling the metal oxide-based working electrode and the porous carbon-based counter electrode, and packaging in electrolyte to obtain the metal oxide-based capacitance type ion diode. The invention provides a method for preparing the metal oxide based capacitive ion diode, which adopts a metal oxide material with intercalation pseudo-capacitance behavior as an electrode material of the capacitive ion diode for the first time, and utilizes the selective storage behavior of anions and cations in electrolyte to realize the unidirectional energy storage of the device.
Description
Technical Field
The invention discloses a metal oxide-based capacitive ion diode, a preparation method and application thereof, in particular relates to a metal oxide-based capacitive ion diode, a preparation method and application thereof in an ion/electron coupling circuit, and belongs to the field of electrochemical energy storage and the field of emerging ion/electron coupling circuits.
Background
The capacitive ion diode is a novel electrochemical functional device based on the super capacitor, has a device structure similar to the super capacitor and one-way conduction characteristics of the semiconductor diode, is considered to be a basic element with the most potential for constructing a novel ion circuit, and has wide application prospect in the technical fields of future living diagnosis and treatment, man-machine interface, neural network interaction and the like. In 2019, professor Stefan kasdel, university of de-daston industry, first proposed the concept of capacitive ion diodes and utilized the size screening effect of porous carbon electrodes on anions and cations to construct the first capacitive ion diode. The capacitive ion diode exhibits electrochemical behavior of unidirectional energy storage and unidirectional conduction voltammetry similar to that of a conventional semiconductor diode thanks to the differential storage behavior of the microporous carbon electrode to anions and cations. The special properties are expected to expand the use prospect of the traditional super capacitor to a new technical field, so that the super capacitor plays an important role in aspects of electric energy transmission, signal transmission, logic operation and the like, and therefore, the super capacitor is widely focused by people.
However, the capacitive ion diode based on the ion screening effect has strict requirements on the pore structure of the porous carbon electrode, and in order to enable the device to have higher rectification ratio, the porous carbon electrode should have a single pore size distribution, which clearly greatly increases the manufacturing cost of the porous carbon electrode, especially the pure microporous carbon electrode, and meanwhile, the limited mass ratio capacitance and the lower bulk density of the carbon material greatly limit the unidirectional energy storage density of the constructed capacitive ion diode, which is unfavorable for the efficient and stable operation of the capacitive ion diode for a long time.
Disclosure of Invention
The purpose of the application is to provide a metal oxide based capacitive ion diode and a preparation method and application thereof, so that the technical problems of low unidirectional energy storage density and high cost of the conventional capacitive ion diode are solved.
The first aspect of the invention provides a method for preparing a metal oxide based capacitive ion diode, comprising the following steps:
preparing a metal oxide-based working electrode and a porous carbon-based counter electrode, wherein the metal oxide used by the metal oxide-based working electrode is a metal oxide with intercalation pseudo-capacitance behavior;
preparing an electrolyte, wherein only one ion type in anions and cations of the electrolyte can be stored in the metal oxide;
and assembling the metal oxide-based working electrode and the porous carbon-based counter electrode, placing the assembled metal oxide-based working electrode and the porous carbon-based counter electrode in the electrolyte, and then packaging to obtain the metal oxide-based capacitive ion diode.
Preferably, the loading amount of the porous carbon-based counter electrode active material is 1 to 2 times that of the metal oxide-based working electrode active material.
Preferably, the metal oxide-based working electrode is prepared, specifically comprising:
mixing a metal oxide material with a conductive agent and a binder, and adding a dispersing agent to obtain slurry;
and setting the slurry on a current collector to obtain the metal oxide-based working electrode.
Preferably, the mass ratio of the metal oxide material to the conductive agent to the binder is 6-9:1-3:1.
Preferably, the metal oxide material is at least one of niobium pentoxide, molybdenum trioxide, tungsten trioxide and titanium dioxide.
Preferably, a porous carbon-based counter electrode is prepared, specifically comprising:
mixing a porous carbon material with a conductive agent and a binder, and adding a dispersing agent to obtain slurry;
and setting the slurry on a current collector to obtain the porous carbon-based counter electrode.
Preferably, the mass ratio of the porous carbon material, the conductive agent and the binder is 6-9:1-3:1.
Preferably, the electrolyte in the electrolyte is an inorganic salt or an organic salt;
the concentration of the electrolyte is 0.001-10 mol/L.
The second aspect of the invention provides a metal oxide based capacitive ion diode, which is prepared by the preparation method of the metal oxide based capacitive ion diode.
A third aspect of the present invention provides an ion/electron coupling circuit in which the metal oxide based capacitive ion diode described above is used.
Compared with the prior art, the metal oxide based capacitive ion diode and the preparation method and application thereof have the following beneficial effects:
the invention provides a method for preparing the metal oxide based capacitive ion diode, which adopts a metal oxide material with intercalation pseudo-capacitance behavior as an electrode material of the capacitive ion diode for the first time, and utilizes the selective storage behavior of anions and cations in electrolyte to realize the unidirectional energy storage of the device.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a metal oxide based capacitive ion diode according to an embodiment of the present invention;
FIG. 2 is a low power scanning electron microscope image of niobium pentoxide material in example 1 of the present invention;
FIG. 3 is a high power scanning electron microscope image of the niobium pentoxide material in example 1 of the present invention;
FIG. 4 is an X-ray diffraction chart of the niobium pentoxide material in example 1 of the present invention;
FIG. 5 is a cyclic voltammogram of a niobium pentoxide electrode in example 1 of the present invention, wherein (a) is a sweep rate of 0.5mV s -1 、0.8mV s -1 、1.0mV s -1 Cyclic voltammograms of the niobium pentoxide electrode; (b) At a sweeping speed of 2.0mV s -1 、5.0mV s -1 、8.0mV s -1 Cyclic voltammograms of the niobium pentoxide electrode;
FIG. 6 is a constant current charge/discharge curve of a niobium pentoxide electrode in example 1 of the present invention, wherein (a) is a current density of 0.1Ag -1 、0.2Ag -1 、0.5Ag -1 、0.8Ag -1 、1Ag -1 Constant current charge-discharge curve of niobium pentoxide electrode; (b) At a current density of 1Ag -1 、2Ag -1 、3Ag -1 、4Ag -1 、5Ag -1 Constant current charge-discharge curve of niobium pentoxide electrode;
FIG. 7 is a first class of rectification ratios of the niobium pentoxide electrode in example 1 of the present invention;
FIG. 8 is a second type of rectification ratio of the niobium pentoxide electrode in example 1 of the present invention;
FIG. 9 is a mass specific capacitance of the niobium pentoxide electrode in example 1 of the present invention;
fig. 10 is a cyclic voltammogram of a niobium pentoxide-based capacitive ion diode in example 1 of the present invention.
Detailed Description
The first aspect of the invention provides a method for preparing a metal oxide based capacitive ion diode, comprising the following steps:
and step 1, preparing a metal oxide-based working electrode and a porous carbon-based counter electrode, wherein the metal oxide used for the metal oxide-based working electrode is a metal oxide with intercalation pseudocapacitance behavior.
In the embodiment of the invention, two schemes can be adopted for preparing the metal oxide base working electrode:
the first scheme is as follows: mixing a metal oxide material, a conductive agent and a binder in a certain proportion, adding a certain amount of dispersing agent, setting the slurry on a current collector, fully drying in a vacuum oven, and cutting to obtain the metal oxide-based working electrode.
The second scheme is as follows: the metal oxide material and the conductive agent are mixed according to a certain proportion, and then a certain amount of dispersing agent is added, so that the self-supporting metal oxide-based working electrode is prepared, and the flexible diode can be assembled by using the self-supporting metal oxide-based working electrode.
The metal oxide material in the embodiment of the invention is niobium pentoxide (Nb) 2 O 5 ) Molybdenum trioxide (MoO) 3 ) Tungsten trioxide (WO) 3 ) Titanium dioxide (TiO) 2 ) At least one of the intercalation pseudocapacitance materials. The metal oxide material may be, for example, niobium pentoxide (Nb) 2 O 5 ) Tungsten trioxide (WO) 3 ) Titanium dioxide (TiO) 2 ) One of them, or molybdenum trioxide (MoO 3 ) With niobium pentoxide (Nb) 2 O 5 ) Tungsten trioxide (WO) 3 ) Titanium dioxide (TiO) 2 ) At least one of the materials. The material can selectively store anions and cations in the electrolyte, so that the unidirectional energy storage density of the metal oxide based capacitive ion diode is high.
The conductive agent in the embodiment of the invention comprises, but is not limited to, conductive carbon black (Super-P), ketjen black, acetylene black, single-wall or multi-wall carbon nanotubes, graphene nanoplatelets, high-crystalline graphite powder; binders include, but are not limited to, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylonitrile, sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, styrene-butadiene rubber, and sodium alginate; dispersants include, but are not limited to, deionized water, ethanol, ethylene glycol, acetone, acetonitrile, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide, dimethylsulfoxide. The conductive agent, the binder and the dispersing agent of the components are matched with the metal oxide material to perform synergistic effect, so that the metal oxide-based working electrode can be ensured to selectively store anions and cations in the electrolyte, and the metal oxide-based capacitive ion diode has high unidirectional energy storage density, high rectification ratio and high stability.
The mass ratio of the metal oxide material, the conductive agent, and the binder is 6 to 9:1 to 3:1, for example, 6:1:1, 6:2:1, 6:3:1, 7:1:1, 7:2:1, 7:3:1, 8:1:1, 8:2:1, 8:3:1, 9:1:1, 9:2:1, or 9:3:1, etc., and preferably 8:1:1. The prepared metal oxide based capacitive ion diode has higher unidirectional energy storage density, mass specific capacitance and volume specific capacitance, and can ensure long-time efficient and stable operation. When the second scheme is adopted, the mass ratio of the metal oxide material to the conductive agent is 6-9:1-3.
In the embodiment of the invention, the method for arranging the slurry on the current collector can be a coating method, and self-supporting electrodes can also be prepared by adopting methods of electrostatic spinning, interface assembly, vacuum filtration and the like. The method is simple, has strong operability and low cost, and the obtained working electrode has good stability. Wherein the current collector includes, but is not limited to, aluminum foil, copper foil, titanium foil, nickel foil, gold sheet, platinum sheet, stainless steel mesh, nickel foam, copper foam, graphite foil, carbon paper, carbon cloth. The current collector made of the material has small internal resistance, and can collect the current generated by the metal oxide material to form larger current for external output.
In the embodiment of the invention, two schemes can be adopted for preparing the porous carbon-based counter electrode:
the first scheme is as follows: mixing a porous carbon material with a conductive agent and a binder, and adding a dispersing agent to obtain slurry;
and (3) arranging the slurry on a current collector, and then cutting the current collector after the current collector is fully dried in a vacuum oven to obtain the porous carbon-based counter electrode.
The second scheme is as follows: after a certain amount of dispersing agent is added into the porous carbon material, a self-supporting porous carbon-based counter electrode is prepared, and then the self-supporting porous carbon-based counter electrode and a metal oxide-based working electrode can be assembled to obtain the flexible diode.
The porous carbon material used in the embodiment of the invention can be at least one of commercial activated carbon, biomass carbon, macromolecule derivatization carbon, organic micromolecule derivatization carbon, graphene, graphite alkyne, carbon nano tube and the like. The porous carbon material is easy to obtain, and the performance of the counter electrode prepared by using the porous carbon material is stable.
The conductive agent in the embodiment of the invention comprises, but is not limited to, conductive carbon black (Super-P), ketjen black, acetylene black, single-wall or multi-wall carbon nanotubes, graphene nanoplatelets, high-crystalline graphite powder; binders include, but are not limited to, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyacrylonitrile, sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, styrene-butadiene rubber, and sodium alginate; dispersants include, but are not limited to, deionized water, ethanol, ethylene glycol, acetone, acetonitrile, propylene carbonate, N-methylpyrrolidone, N-dimethylformamide, dimethylsulfoxide. The conductive agent, the binder and the dispersing agent of the components are matched with the porous carbon material to realize synergistic effect, so that the prepared porous carbon-based counter electrode has good conductivity and multiple holes, and is convenient for transferring electrons and transmitting ions.
The mass ratio of the porous carbon material to the conductive agent to the binder is 6-9:1-3:1, for example, the mass ratio can be 6:1:1, 6:2:1, 6:3:1, 7:1:1, 7:2:1, 7:3:1, 8:1:1, 8:2:1, 8:3:1, 9:1:1, 9:2:1 or 9:3:1, and the like, and the porous carbon-based counter electrode prepared under the content is preferably 8:1:1, has good conductivity and more holes, is convenient for transferring electrons and transmitting ions, so that the unidirectional energy storage density, the mass ratio capacitance and the volume ratio capacitance of the metal oxide-based capacitive ion diode are all higher, and the long-time efficient and stable operation of the metal oxide-based capacitive ion diode can be realized.
In the embodiment of the invention, the method for arranging the slurry on the current collector can be a coating method, and self-supporting electrodes can also be prepared by adopting methods of electrostatic spinning, interface assembly, vacuum filtration and the like. The method is simple, has strong operability and low cost, and the obtained counter electrode has good stability. Wherein the current collector includes, but is not limited to, aluminum foil, copper foil, titanium foil, nickel foil, gold sheet, platinum sheet, stainless steel mesh, nickel foam, copper foam, graphite foil, carbon paper, carbon cloth. The current collector made of the material has small internal resistance, and can collect the current generated by the porous carbon material to form larger current for external output.
In order to ensure that the finally constructed capacitive ion diode can work efficiently, the loading capacity of the porous carbon-based counter electrode active material in the embodiment of the invention is 1-10 times, preferably 1-2 times, that of the metal oxide-based working electrode active material.
And 2, preparing electrolyte, wherein only one ion type in anions and cations of the electrolyte can be stored in the metal oxide.
In the embodiment of the invention, the crystal structure and electrochemical characteristics of the metal oxide are combined, the electrolyte in the electrolyte is inorganic salt or organic salt, and then the electrolyte is dissolved in a solvent to obtain the electrolyte. The embodiment of the invention can also directly select the ionic liquid as the electrolyte. The selection standard of the inorganic salt or the organic salt is that one of anions and cations and only one of the anions can be efficiently stored in the active material of the working electrode; the selection standard of the solvent is that the solvent has good dissolving capacity for the inorganic salt or the organic salt and good electrochemical oxidation resistance or reduction resistance; the concentration of the electrolyte is selected according to the selection standard, so that the electrolyte prepared by the method has higher ionic conductivity and wider electrochemical window.
Inorganic salts include, but are not limited to, lithium, sodium, potassium, zinc, magnesium, calcium, aluminum sulfate, nitrate, phosphate, perchlorate, tetrafluoroborate, hexafluorophosphate, bis-fluorosulfonyl imide, trifluoromethane sulfonate, trifluoromethane sulfonyl imide salts, and chlorides, bromides, iodides; organic salts include, but are not limited to, quaternary ammonium, imidazole, pyrrole, tetrafluoroborate of quaternary phosphonium cations, hexafluorophosphate, trifluoromethanesulfonate, trifluoromethanesulfonyl imide salts, and chloride, bromide, iodide. The selection basis is that one ion and only one ion in anions and cations of the inorganic salt or the organic salt can be efficiently stored in the metal oxide material.
In embodiments of the present invention, solvents used to formulate the electrolyte include, but are not limited to, water, acetonitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane. In order to ensure that the prepared electrolyte has good electrochemical stability and high ionic conductivity, the choice of the solvent is not limited to a single solvent, two or more mixed solvents can be selected according to the requirements, and organic micromolecules with specific functions or inorganic salt additives can be introduced.
Further, in the embodiment of the invention, the concentration of the electrolyte is 0.001-10 mol/L, and in the concentration range, the prepared electrolyte has good electrochemical stability and higher ionic conductivity.
and assembling the metal oxide-based working electrode and the porous carbon-based counter electrode in a lamination mode or a winding mode, injecting the prepared electrolyte into the assembled metal oxide-based working electrode and the porous carbon-based counter electrode, and packaging the whole device to obtain the metal oxide-based capacitive ion diode.
The device morphology of the metal oxide based capacitive ion diode obtained by the invention comprises, but is not limited to, button type, sandwich type, soft package type and plane interdigital type.
The invention provides a one-way energy storage key of the capacitive ion diode based on the deep analysis of the working principle of the porous carbon-based capacitive ion diode, which is characterized in that electrode materials are used for selectively storing anions and cations, and the screening effect of metal oxide materials on the anions and cations is innovatively utilized to develop the capacitive ion diode with higher performance, so that the limitation of a material system on each performance of the capacitive ion diode is broken.
The preparation technology of the metal oxide material and the porous carbon material used in the method is mature, simple and easy to obtain, low in cost and suitable for mass production;
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 large-scale production and preparation and low cost.
The second aspect of the invention provides a metal oxide based capacitive ion diode, which is prepared by the preparation method of the metal oxide based capacitive ion diode.
The metal oxide based capacitive ion diode at least comprises a metal oxide based working electrode, a porous carbon based counter electrode and a wide potential window electrolyte, wherein the working principle of unidirectional energy storage is mainly based on the selective storage behavior of the metal oxide electrode to anions and cations of the electrolyte, namely ion screening effect.
The metal oxide based capacitive ion diode constructed by the method has the advantages of high rectification ratio, high specific capacitance, high energy density and excellent cycling stability, and the comprehensive performance is far superior to that of the existing porous carbon based capacitive ion diode, so that the spanning type improvement of the comprehensive performance of the capacitive ion diode is realized.
A third aspect of the present invention provides an ion/electron coupling circuit in which the metal oxide based capacitive ion diode described above is used. The ion/electron coupling circuit using the metal oxide based capacitance type ion diode has very wide practical application prospect in the technical fields of living diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
The technical scheme of the present invention will be described with reference to the specific embodiments, but the scope of the present invention is not limited thereto. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In all the following examples, niobium pentoxide materials were prepared by the "hydrothermal+annealing" method, and the specific preparation process is as follows:
400mg of niobium pentachloride (NbCl) 5 ) Dissolved in 40mL of ethylene glycol while 800mg of hexamethylenetriamine was dissolved in 40mL of deionized water. The two solutions were mixed under magnetic stirring for 20min, after which the mixture was transferred to a 100mL hydrothermal kettle, held at 200 ℃ for 12 hours, and then cooled naturally to room temperature. The obtained product is repeatedly centrifugally washed by ethanol and deionized water, and then is dried in a blast oven at 60 ℃ to obtain pale yellow powder. Heating the pale yellow powder to 600deg.C in air atmosphere, maintaining for 2 hr, and naturally cooling to room temperature to obtain white Nb 2 O 5 And (3) powder.
In all of the following examples, the characterization and testing methods used were as follows:
1) Scanning electron microscope: and observing the microscopic morphology of the niobium pentoxide material.
2) X-ray diffractometer: and testing the X-ray diffraction pattern of the niobium pentoxide material.
3) Electrochemical workstation: and testing cyclic volt-ampere curves and constant-current charge-discharge curves of the niobium pentoxide electrode and the niobium pentoxide-based capacitance type ion diode.
Example 1
Firstly, dispersing the prepared niobium pentoxide powder material, super-P and polyvinylidene fluoride in N-methyl pyrrolidone according to a mixing ratio of 8:1:1, uniformly coating the slurry on a titanium foil, and controlling the loading amount of active substances to be 1mg/cm 2 And drying in a vacuum oven and cutting to obtain the niobium pentoxide-based working electrode.
Secondly, dispersing commercial active carbon, acetylene black and polytetrafluoroethylene in ethanol according to a mixing ratio of 8:1:1, uniformly coating the slurry on a stainless steel mesh, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a vacuum oven and cutting to obtain the active carbon-based counter electrode.
Third step, lithium hexafluorophosphate (LiPF) 6 ) As electrolyte, a mixed solution (volume ratio of 1:1:1) of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is used as a solvent to prepare 1mol/L electrolyte; in the electrolyte, there are and only Li + Can be stored in the niobium pentoxide electrode with high efficiency, so that the niobium pentoxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the niobium pentoxide-based working electrode and the active carbon-based counter electrode into a button cell, injecting prepared lithium hexafluorophosphate electrolyte into the button cell, and then packaging the whole device by a cell sealing machine to obtain the niobium pentoxide-based capacitive ion diode.
As shown in fig. 2, the niobium pentoxide prepared by the method of the present embodiment has a micro-morphology of nanoflower and has a very uniform size, with a diameter of about 2 to 3 μm. From the enlarged scanning electron microscope image, the niobium pentoxide nanoflower is seenThe highly curved folded nanoplatelets are assembled (fig. 3), giving them a high specific surface area, allowing them to be in full contact with the electrolyte. Further X-ray diffraction test revealed (FIG. 4) that the crystal form of niobium pentoxide was orthorhombic, T-Nb 2 O 5 Is a typical intercalation pseudocapacitance material. As can be seen from the cyclic voltammogram shown in fig. 5, the niobium pentoxide electrode shows a very remarkable ion screening effect, namely, a higher charge storage current in a low potential region (1-2.5V), which indicates that lithium ions in the electrolyte can be efficiently stored. In the high potential region (2.5 to 4V), the niobium pentoxide electrode showed only a very weak electric double layer capacitance, indicating that hexafluorophosphate ions in the electrolyte cannot be effectively stored inside the niobium pentoxide electrode due to the ion screening effect. As can be seen from the constant current charge-discharge curve shown in fig. 6, the charge storage capacity of the niobium pentoxide electrode is mainly concentrated in the low potential region of the lithium ion contribution capacity, and this phenomenon further indicates that the niobium pentoxide electrode has good selective storage behavior for anions and cations in the electrolyte. From the cyclic voltammogram, the first type of rectification ratio of the niobium pentoxide electrode can be calculated to be as high as 79 (fig. 7), which is much higher than that of the previous porous carbon system (-10). The second type of rectification ratio calculated from the constant current charge-discharge curve is also as high as 97.6% (fig. 8), still higher than that of the porous carbon system (-80%). Meanwhile, the niobium pentoxide electrode shows ultra-high mass specific capacitance of 659C/g at a current density of 0.1A/g (FIG. 9), which is also higher than that of the previous porous carbon system<100C/g). The excellent ion rectification performance enables the capacitive ion diode assembled by the niobium pentoxide electrodes to show ideal unidirectional energy storage behavior (figure 10), the working voltage of the capacitive ion diode can reach +/-2V, and the capacitive ion diode has good practical application prospects in the technical fields of smart power grids, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like based on ion/electron coupling circuits in the future.
Example 2
Firstly, mixing and dispersing the niobium pentoxide powder material, ketjen black and sodium alginate in deionized water according to a ratio of 7:2:1, and uniformly coating the slurry on the deionized waterThe loading of the active substance on the graphite foil is controlled to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the niobium pentoxide-based working electrode.
Secondly, dispersing commercial carbon nano-tubes, super-P and sodium carboxymethyl cellulose in deionized water according to a ratio of 7:2:1, uniformly coating the slurry on a titanium foil, and controlling the loading amount of active substances to be 3mg/cm 2 And drying in a blast oven and cutting to obtain the carbon nanotube-based counter electrode.
Thirdly, selecting lithium triflimide (LiTFSI) as an electrolyte and deionized water as a solvent to prepare a high-concentration salt electrolyte with the concentration of 21 mol/kg; in the electrolyte, there are and only Li + Can be stored in the niobium pentoxide electrode with high efficiency, so that the niobium pentoxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the niobium pentoxide-based working electrode and the carbon nano tube-based counter electrode in a lamination mode, injecting prepared lithium trifluoromethanesulfonyl imide high-concentration salt electrolyte into the assembled working electrode, and then packaging the whole device by using a sealing film to obtain the niobium pentoxide-based capacitance type ion diode.
The niobium pentoxide electrode prepared by the method has a very remarkable ion screening effect in the lithium trifluoromethanesulfonyl imide electrolyte, namely, the electrode shows higher charge storage current in a low potential zone, and only shows very weak electric double layer capacitance in a high potential zone, which indicates that the lithium trifluoromethanesulfonyl imide ions in the electrolyte cannot be effectively stored in the niobium pentoxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the niobium pentoxide electrode is mainly concentrated in a low potential region of the lithium ion contribution capacity, which further indicates that the niobium pentoxide electrode has good selective storage behavior for anions and cations in the electrolyte. The calculated first class rectification ratio of the niobium pentoxide electrode in the lithium triflimide electrolyte is up to 95, the second class rectification ratio is up to 98.5%, the mass specific capacitance is up to 575C/g, and the values are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the niobium pentoxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 3
Firstly, dispersing the niobium pentoxide powder material, acetylene black and styrene-butadiene rubber mixed materials in a ratio of 7:2:1 in deionized water, uniformly coating the slurry on a gold sheet, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a blast oven to obtain the niobium pentoxide-based working electrode.
Secondly, dispersing the macromolecular derivatization carbon, super-P and polytetrafluoroethylene in ethanol according to a mixing ratio of 8:1:1, uniformly coating the slurry on foam nickel, and controlling the loading amount of active substances to be 4mg/cm 2 And drying in a blast oven and cutting to obtain the polymer derivative carbon-based counter electrode.
Third step, lithium perchlorate (LiClO) 4 ) As an electrolyte, a mixed solution (volume ratio of 1:1) of ethylene carbonate and propylene carbonate is used as a solvent to prepare 2mol/L electrolyte; in the electrolyte, there are and only Li + Can be stored in the niobium pentoxide electrode with high efficiency, so that the niobium pentoxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the niobium pentoxide-based working electrode and the macromolecule derivatization carbon-based counter electrode into a button cell, injecting the prepared lithium perchlorate electrolyte into the button cell, and then packaging the whole device by a cell sealing machine to obtain the niobium pentoxide-based capacitance type ion diode.
The niobium pentoxide electrode prepared by the method has a very remarkable ion screening effect in lithium perchlorate electrolyte, namely higher charge storage current is shown in a low potential zone, and only very weak double-layer capacitance is shown in a high potential zone, which indicates that perchlorate ions in the electrolyte cannot be effectively stored in the niobium pentoxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the niobium pentoxide electrode is mainly concentrated in a low potential region of the lithium ion contribution capacity, which further indicates that the niobium pentoxide electrode has good selective storage behavior for anions and cations in the electrolyte. The calculated first type rectification ratio of the niobium pentoxide electrode in the lithium perchlorate electrolyte is up to 128, the second type rectification ratio is up to 97.8%, the mass ratio capacitance is up to 712C/g, and the values are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the niobium pentoxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 4
Firstly, dispersing the prepared niobium pentoxide powder material, graphene nanosheets and polyvinylidene fluoride in N-methyl pyrrolidone according to a mixture ratio of 7:2:1, uniformly coating the slurry on a copper foil, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the niobium pentoxide-based working electrode.
Secondly, dispersing commercial activated carbon, super-P and polyvinylidene fluoride in N-methyl pyrrolidone according to a mixture ratio of 7:2:1, uniformly coating the slurry on an aluminum foil, and controlling the loading amount of active substances to be 3mg/cm 2 And drying in a blast oven and cutting to obtain the active carbon-based counter electrode.
Thirdly, lithium bis (fluorosulfonyl) imide (LiFSI) is used as an electrolyte, and a mixed solution of diethylene glycol dimethyl ether and 1, 3-dioxolane (volume ratio is 1:1) is used as a solvent to prepare an electrolyte with the concentration of 1 mol/L; in the electrolyte, there are and only Li + Can be stored in the niobium pentoxide electrode with high efficiency, so that the niobium pentoxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the niobium pentoxide-based working electrode and the active carbon-based counter electrode into a button cell, injecting the prepared lithium bis (fluorosulfonyl) imide electrolyte into the button cell, and then packaging the whole device by a cell sealing machine to obtain the niobium pentoxide-based capacitive ion diode.
The niobium pentoxide electrode prepared by the method has a very remarkable ion screening effect in the lithium bis (fluorosulfonyl) imide electrolyte, namely, the electrode shows higher charge storage current in a low potential region, and only shows very weak electric double layer capacitance in a high potential region, which indicates that the bis (fluorosulfonyl) imide ions in the electrolyte cannot be effectively stored in the niobium pentoxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the niobium pentoxide electrode is mainly concentrated in a low potential region of the lithium ion contribution capacity, which further indicates that the niobium pentoxide electrode has good selective storage behavior for anions and cations in the electrolyte. The calculated first class rectification ratio of the niobium pentoxide electrode in the lithium difluorosulfimide electrolyte is up to 72, the second class rectification ratio is up to 96.6%, the mass specific capacitance is up to 616C/g, and the values are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the niobium pentoxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 5
Firstly, dispersing the prepared molybdenum trioxide powder material, super-P and polytetrafluoroethylene mixed materials according to a ratio of 8:1:1 in ethanol, uniformly coating the slurry on a titanium foil, and controlling the loading amount of active substances to be 1mg/cm 2 And drying in a blast oven and cutting to obtain the molybdenum trioxide-based working electrode.
Secondly, dispersing commercial active carbon, super-P and polytetrafluoroethylene in ethanol according to a mixing ratio of 8:1:1, uniformly coating the slurry on a graphite foil, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the active carbon-based counter electrode.
Third step, sodium perchlorate (NaClO) 4 ) As electrolyte, deionized water is used as solvent to prepare 17mol/kg high-concentration salt electrolyte; in the electrolyte, there is Na only + Can be high in molybdenum trioxide electrodeThe molybdenum trioxide electrode is effectively stored, so that the molybdenum trioxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the molybdenum trioxide-based working electrode and the active carbon-based counter electrode in a lamination mode, injecting prepared sodium perchlorate high-concentration salt electrolyte into the molybdenum trioxide-based working electrode and the active carbon-based counter electrode, and then packaging the whole device by using a sealing film to obtain the molybdenum trioxide-based capacitive ion diode.
The molybdenum trioxide-based working electrode prepared by the method has a very remarkable ion screening effect in sodium perchlorate electrolyte, namely, higher charge storage current is shown in a low potential interval, and only very weak double-layer capacitance is shown in a high potential interval, which indicates that perchlorate ions in the electrolyte cannot be effectively stored in the molybdenum trioxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated in a low potential region of the sodium ion contribution capacity, which further indicates that the molybdenum trioxide electrode has good selective storage behavior for anions and cations in the electrolyte. The first type rectification ratio of the molybdenum trioxide electrode in the sodium perchlorate electrolyte is up to 136, the second type rectification ratio is up to 97.2%, the mass ratio capacitance is up to 448C/g, and the values are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the molybdenum trioxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 6
Firstly, mixing the molybdenum trioxide powder material and the carbon nano tube according to the ratio of 9:1, ultrasonically dispersing the mixture in N, N-dimethylformamide, and then carrying out vacuum suction filtration to obtain a self-supporting molybdenum trioxide membrane electrode, wherein the loading amount of active substances is controlled to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the molybdenum trioxide-based working electrode.
Secondly, dispersing commercial carbon nano-tubes in N, N-dimethylformamide by ultrasonic, and obtaining the carbon nano-tubes by adopting the same vacuum filtration methodSelf-supporting carbon nano tube membrane electrode, and controlling the loading amount of active substances to be 4mg/cm 2 And drying in a blast oven and cutting to obtain the carbon nanotube-based counter electrode.
Thirdly, lithium chloride (LiCl) is selected as electrolyte, deionized water is selected as solvent, and polyvinyl alcohol is introduced to gel the electrolyte, so that 1mol/L gel electrolyte is prepared; in the gel electrolyte, there are and only Li + Can be stored in the molybdenum trioxide membrane electrode with high efficiency, so that the molybdenum trioxide membrane electrode can show obvious screening effect of anions and cations.
And fourthly, assembling the self-supporting molybdenum trioxide-based working electrode and the self-supporting carbon nano tube-based counter electrode in a lamination mode, coating a lithium chloride gel electrolyte between the two electrodes, and packaging the whole device by using a sealing film to obtain the flexible molybdenum trioxide-based capacitance type ion diode.
The molybdenum trioxide membrane electrode prepared by the method has a very remarkable ion screening effect in the lithium chloride gel electrolyte, namely, higher charge storage current is shown in a low potential interval, and only very weak double-layer capacitance is shown in a high potential interval, which indicates that chloride ions in the gel electrolyte cannot be effectively stored in the molybdenum trioxide membrane electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the molybdenum trioxide membrane electrode is mainly concentrated in a low potential region of lithium ion contribution capacity, which further indicates that the molybdenum trioxide membrane electrode has good selective storage behavior for anions and cations in the gel electrolyte. The first type rectification ratio of the molybdenum trioxide membrane electrode in the lithium chloride gel electrolyte is up to 58, the second type rectification ratio is up to 94.8%, the mass ratio capacitance is up to 628C/g, and the values are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the molybdenum trioxide membrane electrode to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 7
Firstly, dispersing the prepared titanium dioxide powder material, super-P and polytetrafluoroethylene in ethanol according to a mixing ratio of 6:3:1, uniformly coating the slurry on a graphite foil, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the titanium dioxide-based working electrode.
Secondly, dispersing commercial active carbon, acetylene black and polytetrafluoroethylene in ethanol according to a mixing ratio of 8:1:1, uniformly coating the slurry on graphite foil, and controlling the loading amount of active substances to be 4mg/cm 2 And drying in a blast oven and cutting to obtain the active carbon-based counter electrode.
Thirdly, selecting lithium triflimide (LiTFSI) as an electrolyte and deionized water as a solvent to prepare a high-concentration salt electrolyte with the concentration of 21 mol/kg; in the electrolyte, there are and only Li + Can be stored in the titanium dioxide electrode with high efficiency, so that the titanium dioxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the titanium dioxide-based working electrode and the active carbon-based counter electrode in a lamination mode, injecting prepared high-concentration lithium triflimide salt electrolyte into the titanium dioxide-based working electrode and the active carbon-based counter electrode, and then packaging the whole device by using a sealing film to obtain the titanium dioxide-based capacitance type ion diode.
The titanium dioxide electrode prepared by the method has a very remarkable ion screening effect in the lithium trifluoromethanesulfonyl imide electrolyte, namely, the titanium dioxide electrode shows higher charge storage current in a low potential zone, and only shows very weak electric double layer capacitance in a high potential zone, which indicates that the trifluoromethanesulfonyl imide ions in the electrolyte cannot be effectively stored in the titanium dioxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the titanium dioxide electrode is mainly concentrated in a low potential region of the lithium ion contribution capacity, which further indicates that the niobium pentoxide electrode has good selective storage behavior for anions and cations in the electrolyte. The titanium dioxide electrode has a first type rectification ratio of 188 and a second type rectification ratio of 98.5 percent in the lithium triflimide electrolyte, and has a mass specific capacitance of 484C/g, which are far higher than those of the porous carbon system reported before. The excellent ion rectification performance enables the capacitive ion diode assembled by the titanium dioxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Example 8
Firstly, dispersing the prepared titanium dioxide powder material, ketjen black and sodium carboxymethylcellulose in deionized water according to a ratio of 6:3:1, uniformly coating the slurry on a copper foil, and controlling the loading amount of active substances to be 1mg/cm 2 And drying in a blast oven and cutting to obtain the titanium dioxide-based working electrode.
Secondly, dispersing commercial active carbon, super-P and sodium alginate in deionized water according to a ratio of 7:2:1, uniformly coating the slurry on an aluminum foil, and controlling the loading amount of active substances to be 2mg/cm 2 And drying in a blast oven and cutting to obtain the active carbon-based counter electrode.
Third step, lithium hexafluorophosphate (LiPF) 6 ) As electrolyte, a mixed solution (volume ratio of 1:1:1) of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is used as a solvent to prepare 1mol/L electrolyte; in the electrolyte, there are and only Li + Can be stored in the titanium dioxide electrode with high efficiency, so that the titanium dioxide electrode can show obvious anion-cation screening effect.
And fourthly, assembling the titanium dioxide-based working electrode and the active carbon-based counter electrode into a button cell, injecting prepared lithium hexafluorophosphate electrolyte into the button cell, and then packaging the whole device by a cell sealing machine to obtain the titanium dioxide-based capacitive ion diode.
The titanium dioxide electrode prepared by the method has a very remarkable ion screening effect in lithium hexafluorophosphate electrolyte, namely, higher charge storage current is shown in a low potential interval, and only very weak double-layer capacitance is shown in a high potential interval, so that the hexafluorophosphate ions in the electrolyte cannot be effectively stored in the titanium dioxide electrode due to the ion screening effect. Meanwhile, the charge storage capacity of the titanium dioxide electrode is mainly concentrated in a low potential region of the lithium ion contribution capacity, which further indicates that the titanium dioxide electrode has good selective storage behavior for anions and cations in the electrolyte. The titanium dioxide electrode has a first type rectification ratio of up to 163, a second type rectification ratio of up to 97.6, and a mass specific capacitance of up to 518C/g in lithium hexafluorophosphate electrolyte, which are all much higher than the porous carbon systems reported previously. The excellent ion rectification performance enables the capacitive ion diode assembled by the titanium dioxide electrodes to show ideal unidirectional energy storage behavior, and can be widely applied to the technical fields of intelligent power grids based on ion/electron coupling circuits, living body diagnosis and treatment, man-machine interfaces, neural network interaction and the like.
Variations and modifications to the above would be obvious to those skilled in the art to which the invention pertains from the foregoing description of the invention. Accordingly, the present invention includes, but is not limited to, the above embodiments, any equivalent or partial modification under the device construction principle of the present invention, will fall within the protection scope of the present invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A method for preparing a metal oxide based capacitive ion diode, comprising:
preparing a metal oxide-based working electrode and a porous carbon-based counter electrode, wherein the metal oxide used by the metal oxide-based working electrode is a metal oxide with intercalation pseudo-capacitance behavior;
preparing an electrolyte, wherein only one ion type in anions and cations of the electrolyte can be stored in the metal oxide;
and assembling the metal oxide-based working electrode and the porous carbon-based counter electrode, placing the assembled metal oxide-based working electrode and the porous carbon-based counter electrode in the electrolyte, and then packaging to obtain the metal oxide-based capacitive ion diode.
2. The method of manufacturing a metal oxide based capacitive ion diode according to claim 1, wherein the loading amount of the porous carbon based counter electrode active material is 1 to 10 times the loading amount of the metal oxide based working electrode active material.
3. The method for manufacturing a metal oxide based capacitive ion diode according to claim 1, wherein manufacturing a metal oxide based working electrode specifically comprises:
mixing a metal oxide material with a conductive agent and a binder, and adding a dispersing agent to obtain slurry;
and setting the slurry on a current collector to obtain the metal oxide-based working electrode.
4. The method for manufacturing a metal oxide based capacitive ion diode according to claim 3, wherein the mass ratio of the metal oxide material, the conductive agent and the binder is 6-9:1-3:1.
5. The method for manufacturing a metal oxide based capacitive ion diode according to claim 3, wherein the metal oxide material is at least one of niobium pentoxide, molybdenum trioxide, tungsten trioxide, and titanium dioxide.
6. The method for preparing a metal oxide based capacitive ion diode according to claim 1, wherein preparing a porous carbon based counter electrode specifically comprises:
mixing a porous carbon material with a conductive agent and a binder, and adding a dispersing agent to obtain slurry;
and setting the slurry on a current collector to obtain the porous carbon-based counter electrode.
7. The method for preparing a metal oxide based capacitive ion diode according to claim 6, wherein the mass ratio of the porous carbon material, the conductive agent and the binder is 6-9:1-3:1.
8. The method for manufacturing a metal oxide based capacitive ion diode according to claim 1, wherein the electrolyte in the electrolyte solution is an inorganic salt or an organic salt;
the concentration of the electrolyte is 0.001-10 mol/L.
9. A metal oxide based capacitive ion diode prepared by the method of any one of claims 1-8.
10. An ion/electron coupling circuit using the metal oxide based capacitive ion diode of claim 9.
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| JP2019153790A (en) * | 2018-03-05 | 2019-09-12 | 株式会社ジェイテクト | Power storage device |
| CN110676062A (en) * | 2019-10-08 | 2020-01-10 | 中国科学院兰州化学物理研究所 | Electric energy generating and storing device and manufacturing method thereof |
| US20200273949A1 (en) * | 2019-02-21 | 2020-08-27 | Kemet Electronics Corporation | Packages for Power Modules with Integrated Passives |
| CN115207280A (en) * | 2022-07-25 | 2022-10-18 | 中国科学院上海硅酸盐研究所 | Bipolar electrode based on metal oxide or composite material cathode thereof and bipolar lithium ion battery |
| CN115631950A (en) * | 2022-10-19 | 2023-01-20 | 中山大学 | Pseudo-capacitance-based super capacitor diode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019153790A (en) * | 2018-03-05 | 2019-09-12 | 株式会社ジェイテクト | Power storage device |
| US20200273949A1 (en) * | 2019-02-21 | 2020-08-27 | Kemet Electronics Corporation | Packages for Power Modules with Integrated Passives |
| CN110676062A (en) * | 2019-10-08 | 2020-01-10 | 中国科学院兰州化学物理研究所 | Electric energy generating and storing device and manufacturing method thereof |
| CN115207280A (en) * | 2022-07-25 | 2022-10-18 | 中国科学院上海硅酸盐研究所 | Bipolar electrode based on metal oxide or composite material cathode thereof and bipolar lithium ion battery |
| CN115631950A (en) * | 2022-10-19 | 2023-01-20 | 中山大学 | Pseudo-capacitance-based super capacitor diode and preparation method thereof |
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