CN116230423A - Implantable capacitive ion diode and preparation method and application thereof - Google Patents
Implantable capacitive ion diode and preparation method and application thereof Download PDFInfo
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- CN116230423A CN116230423A CN202310217033.0A CN202310217033A CN116230423A CN 116230423 A CN116230423 A CN 116230423A CN 202310217033 A CN202310217033 A CN 202310217033A CN 116230423 A CN116230423 A CN 116230423A
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- molybdenum trioxide
- porous carbon
- electrolyte
- ion diode
- working electrode
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- 238000000034 method Methods 0.000 claims abstract description 37
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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Images
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electrotherapy Devices (AREA)
Abstract
The invention discloses an implantable capacitance type ion diode, a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a molybdenum trioxide-based working electrode and a porous carbon-based counter electrode; preparing electrolyte, wherein only one ion in anions and cations of the electrolyte can be stored in molybdenum trioxide; and assembling the molybdenum trioxide-based working electrode and the porous carbon-based counter electrode, placing the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode in electrolyte, and then packaging the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode by utilizing a biocompatible material to obtain the implantable capacitive ion diode. The invention provides a method for constructing an implantable capacitive ion diode with high rectification ratio, high stability and good biocompatibility by adopting a molybdenum trioxide pseudo-capacitance material as a working electrode of the capacitive ion diode and combining a biocompatible porous carbon counter electrode and a biocompatible packaging material for the first time, and a logic operation circuit constructed by the implantable capacitive ion diode can efficiently and stably work and has wide application prospect in the technical fields of future living diagnosis and treatment, man-machine interface, neural network interaction and the like.
Description
Technical Field
The invention discloses an implantable capacitive ion diode, a preparation method and application thereof, in particular relates to an implantable capacitive ion diode, a preparation method and application thereof in the aspect of logic operation, and belongs to the field of electrochemical energy storage and emerging ion/electron coupling circuits.
Background
The rapid development of the fields of computer science, brain science, bionic science, material science, flexible electronics and the like in recent years greatly promotes the birth and development of brain-computer interface technology, however, the two-way communication between the human brain and the computer at the present stage is far from reaching the practical level, wherein the main reason is that the human brain and the computer respectively adopt two different information conduction media of ion and electron. The difference on the information carrier enables the two systems of the human brain and the electronic computer to have completely different operation mechanisms, and also brings great challenges for deep fusion and interaction of the two systems.
The advent of ion electronics enabled the organic combination of electron transfer and ion transport in the same circuit, providing a potential medium for information transfer between biological systems and electronic devices. Meanwhile, the ion/electron coupling device based on the ion electronics has an information transmission mode compatible with neurons and a working medium compatible with physiological water solution, so that the ion electronics is the development direction with the most potential for realizing the bidirectional intercommunication of human brain and a computer. Nevertheless, to truly realize information interaction between biological systems and electronic devices, it is also necessary to design and develop devices with logic operation functions to complete information detection, transmission, processing and feedback processes, wherein the most basic components are ion diodes similar to semiconductor diodes. The capacitive ion diode is a novel ion/electron coupling device, has a device structure similar to a super capacitor and the same unidirectional conduction characteristic as a semiconductor diode, and is a basic element with the most potential for constructing an ion/electron coupling circuit.
The unidirectional energy storage characteristic of the conventional capacitive ion diode is mainly based on the size screening effect of the porous carbon electrode on the anions and cations of the electrolyte, but is limited to the defects of the porous carbon electrode, and the conventional capacitive ion diode still has the problems of low rectification ratio, low specific capacitance, poor stability and high manufacturing cost, and cannot meet the practical requirements. In addition, as the development of the capacitive ion diode is still in a starting stage, the biocompatibility of the currently developed device is not considered, so that the device cannot work safely and reliably in an in-vivo environment, and the further development of the capacitive ion diode is greatly limited.
Disclosure of Invention
The present application provides a capacitive ion diode having excellent rectification characteristics and good biocompatibility, so as to solve the problems of low rectification ratio, poor stability, high manufacturing cost and poor biocompatibility of the conventional capacitive ion diode.
The first aspect of the present invention provides a method for preparing an implantable capacitive ion diode, comprising:
preparing a molybdenum trioxide-based working electrode and a porous carbon-based counter electrode;
preparing an electrolyte, wherein only one ion type in anions and cations of the electrolyte can be stored in molybdenum trioxide;
and assembling the molybdenum trioxide-based working electrode and the porous carbon-based counter electrode, placing the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode in the electrolyte, and then packaging the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode by utilizing a biocompatible material to obtain the implantable capacitive ion diode.
Preferably, the loading amount of the porous carbon-based counter electrode active material is 1 to 10 times that of the molybdenum trioxide-based working electrode active material.
Preferably, a molybdenum trioxide-based working electrode is prepared, specifically comprising:
mixing molybdenum trioxide powder 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 molybdenum trioxide-based working electrode.
Preferably, the mass ratio of the molybdenum trioxide powder material, the conductive agent and the binder is 7-9:1-2:1.
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 7-9:1-2:1.
Preferably, the conductive agent comprises one of conductive carbon black, ketjen black, acetylene black, carbon nanotubes and graphene nanoplatelets;
the binder comprises one of polytetrafluoroethylene, sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, sodium alginate and bacterial cellulose;
the dispersing agent comprises one of deionized water, ethanol, ethylene glycol, propylene carbonate and N-methyl pyrrolidone.
Preferably, the electrolyte in the electrolyte is an inorganic salt or an inorganic acid;
the concentration of the electrolyte is 0.001-10 mol/L.
The second aspect of the invention provides an implantable capacitive ion diode, which is prepared by the preparation method of the implantable capacitive ion diode.
A third aspect of the present invention provides a logic circuit in which the implantable capacitive ion diode described above is used.
Compared with the prior art, the implantable capacitive ion diode and the preparation method and application thereof have the following beneficial effects:
the invention firstly proposes to adopt molybdenum trioxide (MoO) with high electrochemical activity and good biocompatibility 3 ) The pseudocapacitance material is used as a working electrode of the capacitive ion diode, and is combined with a biocompatible porous carbon counter electrode and a biocompatible packaging material to construct the high-performance implantable capacitive ion diode. The capacitive ion diode constructed by the scheme has the advantages of high rectification ratio, high stability and good biocompatibility, and the logic operation circuit constructed by the capacitive ion diode can efficiently and stably work and has wide application prospect in the technical fields of future living diagnosis and treatment, man-machine interface and neural network interaction and the like.
Drawings
FIG. 1 is a flow chart of a method for fabricating an implantable capacitive ion diode according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a molybdenum trioxide material according to embodiment 1 of the invention;
FIG. 3 is a transmission electron microscope image of a molybdenum trioxide material according to embodiment 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of a molybdenum trioxide material according to the invention of example 1;
FIG. 5 is a Raman spectrum of a molybdenum trioxide material according to embodiment 1 of the invention;
FIG. 6 is a cyclic voltammogram of a molybdenum trioxide electrode of example 1 of the present invention;
FIG. 7 is a constant current charge-discharge curve of the molybdenum trioxide electrode of example 1 of the present invention;
FIG. 8 is a first class of rectification ratios for the molybdenum trioxide electrode of example 1 of the present invention;
FIG. 9 is a second type of rectification ratio of the molybdenum trioxide electrode of example 1 of the present invention;
FIG. 10 is a schematic diagram of an implantable capacitive ion diode according to embodiment 1 of the present invention;
FIG. 11 is a cyclic voltammogram of an implantable capacitive ion diode according to example 1 of the present invention;
FIG. 12 is a constant current charge-discharge curve of an implantable capacitive ion diode according to example 1 of the present invention;
FIG. 13 is a first class of rectification ratios of the implantable capacitive ion diode of embodiment 1;
FIG. 14 is a second type of rectification ratio of the implantable capacitive ion diode of embodiment 1;
FIG. 15 shows the application of the implantable capacitive ion diode of embodiment 1 of the present invention in AND gates;
fig. 16 shows the application of the implantable capacitive ion diode of embodiment 1 in an or gate.
Detailed Description
The first aspect of the present invention provides a method for preparing an implantable capacitive ion diode, comprising:
and step 1, preparing a molybdenum trioxide-based working electrode and a porous carbon-based counter electrode.
In the embodiment of the invention, two schemes can be adopted for preparing the molybdenum trioxide-based working electrode:
the first scheme is as follows: mixing molybdenum trioxide powder material with a conductive agent and a binder in a certain proportion, adding a certain amount of dispersing agent, setting slurry on a current collector, fully drying in a vacuum oven, and cutting to obtain the molybdenum trioxide-based working electrode.
The second scheme is as follows: mixing molybdenum trioxide powder material with binder in a certain proportion, adding a certain amount of dispersing agent, preparing a film layer, attaching the film layer on a conductive substrate, fully drying in a vacuum oven, and cutting to obtain the molybdenum trioxide-based working electrode. Wherein the material of the conductive substrate is the same as that of the current collector.
The mass ratio of the molybdenum trioxide powder material to the conductive agent to the binder is 7-9:1-2:1, for example, the mass ratio can be 7:1:1, 7:2:1, 8:1:1, 8:2:1, 9:1:1 or 9:2:1, and the like, preferably 8:1:1, and the implantable capacitive ion diode prepared at the content has high rectification ratio and good stability. When the second scheme is used, the mass ratio of the molybdenum trioxide powder material to the binder is 7-9:1, for example, 7:1, 8:1, 9:1, etc.
Further, the micro-morphology of the molybdenum trioxide powder material in the embodiment of the invention can be at least one of nanorods, nanowires, nanobelts, nanosheets, nanoflower, nanoparticles, hollow nanospheres and the like. The molybdenum trioxide powder with the morphology is easier to mix with the conductive agent and the binder uniformly, so that the prepared working electrode has uniform properties everywhere.
The conductive agent in the embodiment of the invention comprises, but is not limited to, conductive carbon black (Super-P), ketjen black, acetylene black, carbon nanotubes and graphene nanoplatelets; binders include, but are not limited to, polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, sodium alginate, and bacterial cellulose; dispersants include, but are not limited to, deionized water, ethanol, ethylene glycol, propylene carbonate, N-methylpyrrolidone. The conductive agent, the binder and the dispersing agent of the components are matched with the molybdenum trioxide powder material to perform synergistic action, so that the rectification ratio and the stability of the implantable capacitive ion diode are further improved.
Current collectors in embodiments of the present invention include, but are not limited to, titanium foil, gold sheet, platinum sheet, 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 molybdenum trioxide to form larger current for external output.
Further, in the embodiment of the invention, the method for disposing the slurry on the current collector may be a coating method, or may be an interface assembly method, a vacuum filtration method, an electrostatic spinning method, or the like, to prepare a self-supporting electrode. The method is simple, has strong operability and low cost, and the obtained working electrode has good stability.
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: mixing porous carbon material with binder in a certain proportion, adding a certain amount of dispersing agent, preparing a film layer, attaching the film layer on a conductive substrate, fully drying in a vacuum oven, and cutting to obtain the porous carbon-based counter electrode. Wherein the material of the conductive substrate is the same as that of the current collector.
In the embodiment of the invention, the mass ratio of the porous carbon material to the conductive agent to the binder is 7-9:1-2:1, for example, the mass ratio can be 7:1:1, 7:2:1, 8:1:1, 8:2:1, 9:1:1 or 9:2:1, and the like, preferably 8:1:1, and the implantable capacitive ion diode prepared at the content has high rectification ratio and good stability. When the second scheme is used, the mass ratio of the porous carbon material to the binder is 7 to 9:1, for example, 7:1, 8:1, 9:1, etc.
The porous carbon material used in the embodiment of the invention can be at least one of commercial activated carbon, biomass 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, carbon nanotubes and graphene nanoplatelets; binders include, but are not limited to, polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, sodium alginate, and bacterial cellulose; dispersants include, but are not limited to, deionized water, ethanol, ethylene glycol, propylene carbonate, N-methylpyrrolidone. The conductive agent, the binder and the dispersing agent of the components are matched with the porous carbon material to cooperate, so that the rectification ratio and the stability of the implantable capacitive ion diode are further improved.
Current collectors in embodiments of the present invention include, but are not limited to, titanium foil, gold sheet, platinum sheet, 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.
Further, in the embodiment of the invention, the method for disposing the slurry on the current collector may be a coating method, or may be an interface assembly method, a vacuum filtration method, an electrostatic spinning method, or the like, to prepare a self-supporting electrode. The method is simple, has strong operability and low cost, and the obtained working electrode has good stability.
In order to ensure that the finally constructed capacitive ion diode can work efficiently, the loading amount of the porous carbon-based counter electrode active material in the embodiment of the invention is 1 to 10 times, preferably 1.5 to 3 times, for example, 1.5 times, 2 times, 2.5 times, 3 times and the like of the loading amount of the molybdenum trioxide-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 molybdenum trioxide.
In the embodiment of the invention, the crystal structure and electrochemical characteristics of the molybdenum trioxide are combined, the electrolyte in the electrolyte is inorganic salt or inorganic acid, and only one ion in anions and cations of inorganic salt or inorganic acid can be efficiently stored in the molybdenum trioxide.
Inorganic salts include, but are not limited to, sodium, potassium, zinc, magnesium, calcium sulfate, nitrate, phosphate, perchlorate, and chloride, iodide; inorganic acids include, but are not limited to, hydrochloric acid, sulfuric acid, phosphoric acid, and perchloric acid.
In order to ensure that the prepared electrolyte has good electrochemical stability and high ionic conductivity, the choice of the solvent of the electrolyte is not limited to a single solvent such as deionized water, two or more mixed solvents can be selected according to requirements, and small molecules or inorganic salt additives with specific functions can be introduced.
In the embodiment of the invention, the concentration of the electrolyte is 0.001-10 mol/L, and in the concentration range, the electrolyte has higher ionic conductivity and wider electrochemical window, so that the rectification ratio and the electrochemical stability of the prepared implantable capacitive ion diode are improved.
and assembling the molybdenum trioxide-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 molybdenum trioxide-based working electrode and the porous carbon-based counter electrode, and then packaging the whole device by using a biocompatible film to obtain the implantable capacitive ion diode with good biocompatibility.
The biocompatible film packaging material is at least one of Polydimethylsiloxane (PDMS), cellulose Acetate (CA), polyvinyl alcohol (PVA), polylactic acid (PLA), polylactic acid-glycolic acid copolymer (PLGA), sodium carboxymethyl cellulose (Na-CMC), polyanhydride, beeswax, fibroin and the like.
From the aspect of material design, the invention innovatively adopts the pseudo-capacitance material of molybdenum trioxide with high electrochemical activity and good biocompatibility as the working electrode of the capacitive ion diode, combines the biocompatible porous carbon counter electrode and the biocompatible packaging material to construct the high-performance implantable capacitive ion diode, and solves the problem that the conventional capacitive ion diode cannot really work safely and reliably in an in-vivo environment due to poor biocompatibility and poor rectifying performance.
The molybdenum trioxide material and the porous carbon material used in the method have the advantages of mature preparation technology, simplicity, easy obtainment and low cost, and are suitable for mass preparation.
The electrode preparation method used in the method has mature process route, good compatibility with the existing electrode production line, suitability for large-scale production and low cost.
The second aspect of the invention provides an implantable capacitive ion diode, which is prepared by the preparation method of the implantable capacitive ion diode.
The implantable capacitive ion diode provided by the embodiment of the invention at least comprises a molybdenum trioxide-based working electrode with high ion screening activity and good biocompatibility, a biocompatible porous carbon-based counter electrode, high-performance electrolyte and a biocompatible packaging material. The working principle of the one-way energy storage of the implantable capacitive ion diode is mainly based on the selective storage behavior of molybdenum trioxide working electrode to electrolyte anions and cations, namely ion screening effect, and the good biocompatibility or the implantable property of the implantable capacitive ion diode benefits from the good biocompatibility of each component material of the device.
The capacitive ion diode constructed by the method has the advantages of high rectification ratio, high stability and good biocompatibility, and the comprehensive performance is far superior to that of the existing porous carbon-based capacitive ion diode.
A third aspect of the present invention provides a logic circuit in which the implantable capacitive ion diode described above is used. The logic operation circuit using the implantable capacitance type ion diode can efficiently and stably work, and has very wide practical application prospect in the technical fields of living diagnosis and treatment, man-machine interface, neural network interaction and the like based on the ion/electron coupling circuit in the future.
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, the molybdenum trioxide material was prepared by hydrothermal method, and the specific preparation method is as follows:
2g of molybdenum powder was added to 10mL of deionized water with stirring, after which 20mL of a 30wt.% hydrogen peroxide solution was slowly added until the solution became pale yellow, and stirring was continued for 30 minutes to complete the reaction. Transferring the solution into a 50mL hydrothermal kettle, reacting for 72 hours at 220 ℃, and repeatedly centrifuging and washing the obtained product with deionized water after the system temperature is reduced to room temperature to obtain the molybdenum trioxide nanowire.
In all of the following examples, the characterization and testing methods used were as follows:
1) Scanning electron microscope: observing the microscopic morphology of the molybdenum trioxide material.
2) Transmission electron microscope: observing the microscopic morphology and lattice structure of the molybdenum trioxide material.
3) X-ray diffractometer: the molybdenum trioxide material was tested for X-ray diffraction pattern.
4) Raman spectrometer: and testing the Raman spectrum of the molybdenum trioxide material.
5) Electrochemical workstation: and testing the cyclic voltammogram curve and constant current charge-discharge curve of the molybdenum trioxide material and the molybdenum trioxide base capacitance type ion diode.
Example 1
Firstly, preparing molybdenum trioxide powder material by a hydrothermal method, dispersing the molybdenum trioxide powder material and super-P, PTFE mixed materials in ethanol according to a 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 working electrode.
In the second step, a counter electrode based on commercial activated carbon was prepared by the same method as described above, and the loading amount of the active material was controlled to 3mg/cm 2 。
Third step, perchloric acid (H)ClO 4 ) Sodium perchlorate (NaClO) 4 ) Wherein the concentration of perchloric acid is 0.2mol/L and the concentration of sodium perchlorate is 9mol/L. In the electrolyte, H + And Na (Na) + Two cations can be stored efficiently in molybdenum trioxide material, while ClO4 - The molybdenum trioxide can show obvious anion-cation screening effect because of steric hindrance and electrostatic repulsion which can not be stored in the molybdenum trioxide material.
Fourthly, assembling the molybdenum trioxide-based working electrode and the porous carbon-based counter electrode in a lamination mode, injecting mixed electrolyte of perchloric acid and sodium perchlorate into the molybdenum trioxide-based working electrode, and then packaging the whole device by using PDMS to obtain the implantable capacitance type ion diode.
The micro-morphology of the molybdenum trioxide prepared by the method is nano wires, the length of the molybdenum trioxide is 3-5 micrometers (figure 2) from a scanning electron microscope image, and the diameter of the molybdenum trioxide is about 100 nanometers (figure 3) from a transmission electron microscope image. From the X-ray diffraction pattern (fig. 4) and raman pattern (fig. 5), it was found that the molybdenum trioxide was orthorhombic molybdenum trioxide, which was a typical intercalation pseudocapacitance material. From the cyclic voltammogram, it can be seen that the molybdenum trioxide electrode has a very remarkable ion screening effect (FIG. 6), i.e., can be applied to H in the electrolyte in the low potential range (-0.2-0.5V) + Na and Na + High-efficiency storage is performed, and ClO4 in the electrolyte is subjected to a high potential range (0.5-1.0V) - Has obvious ion screening effect and can not be effectively stored. It can also be seen from the constant current charge-discharge curve that the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated on H + Na and Na + The low potential region of the ion contribution capacity (fig. 7), this phenomenon further suggests that the molybdenum trioxide electrode has good selective storage behavior for anions and cations in the electrolyte. The first class of rectification ratio of the molybdenum trioxide electrode was calculated from cyclic voltammograms to be as high as 136 (FIG. 8), much higher than the previously reported system (-10). The second type of rectification ratio calculated from the constant current charge-discharge curve is also as high as 98.8% (fig. 9), which is still higher than the existing porous carbon system (-80%). These excellent ionsThe rectifying performance makes the capacitive ion diode assembled by the molybdenum trioxide electrodes (figure 10) show ideal unidirectional energy storage behavior, the device can be normally charged and discharged in forward bias, and the device can hardly store charges in reverse bias (figure 11). Therefore, the capacity of the entire device is also concentrated in the forward bias region, and there is almost no capacity in the reverse bias region (fig. 12). The first class of rectification ratio of the capacitive ion diode is calculated to be 98 (figure 13), and the second class of rectification ratio is calculated to be 98.7 (figure 14), which is far higher than that of the conventional capacitive ion diode. The excellent rectifying performance enables the capacitive ion diode to efficiently and stably work in two types of logic operation circuits, namely an AND gate (figure 15) and an OR gate (figure 16), so that the capacitive ion diode has good practical application prospect 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, preparing molybdenum trioxide powder material by a hydrothermal method, dispersing the molybdenum trioxide powder material, acetylene black and sodium alginate in deionized water according to a mixing ratio of 7:2:1, 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 vacuum oven and cutting to obtain the working electrode.
Secondly, preparing a counter electrode based on the carbon nano tube by adopting the same method, and controlling the loading amount of the active substance to be 5mg/cm 2 。
Third step, magnesium chloride (MgCl) is selected 2 ) The solution was used as an electrolyte at a concentration of 1mol/L. In the electrolyte, mg 2+ Can be efficiently stored in molybdenum trioxide material, and Cl - The molybdenum trioxide can show obvious anion-cation screening effect because of steric hindrance and electrostatic repulsion which can not be stored in the molybdenum trioxide material.
And fourthly, assembling the molybdenum trioxide-based working electrode and the carbon nano tube-based counter electrode in a lamination mode, injecting magnesium chloride electrolyte into the molybdenum trioxide-based working electrode and the carbon nano tube-based counter electrode, and then packaging the whole device by polylactic acid (PLA) to obtain the implantable capacitance type ion diode.
The molybdenum trioxide-based electrode prepared by the method of the embodiment shows very remarkable ion screening effect in magnesium chloride electrolyte, namely the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated on Mg 2+ Low potential region contributing to capacity, while in Cl - The high potential region contributing to the capacity shows only a very weak electric double layer capacitance. The first type of rectification ratio of the molybdenum trioxide electrode in the magnesium chloride electrolyte is up to 64, the second type of rectification ratio is up to 95.8 percent, and the values are far higher than those of the 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, namely the device can be normally charged and discharged only in forward bias, and the device can hardly store charges in reverse bias. Meanwhile, the capacitive ion diode can efficiently and stably work in a classical logic operation circuit of an AND gate type and an OR gate type, and has good practical application prospect.
Example 3
Firstly, preparing molybdenum trioxide powder material by a hydrothermal method, dispersing the molybdenum trioxide powder material, ketjen black and polyethylene oxide in deionized water according to a mixing ratio of 8:1:1, uniformly coating the slurry on a gold sheet, and controlling the loading amount of active substances to be 1.5mg/cm 2 And drying in a vacuum oven to obtain the working electrode.
Secondly, preparing a counter electrode based on graphene by adopting the same method, and controlling the loading amount of active substances to be 3mg/cm 2 。
Third step, sodium sulfate (Na 2 SO 4 ) The solution was used as an electrolyte at a concentration of 0.5mol/L. In the electrolyte, na + Can be efficiently stored in molybdenum trioxide material, while SO 4 2- The molybdenum trioxide can show obvious anion-cation screening effect because of steric hindrance and electrostatic repulsion which can not be stored in the molybdenum trioxide material.
And fourthly, assembling the molybdenum trioxide-based working electrode and the graphene-based counter electrode in a lamination mode, injecting sodium sulfate electrolyte into the molybdenum trioxide-based working electrode and the graphene-based counter electrode, and then packaging the whole device by polylactic acid-glycolic acid copolymer (PLGA) to obtain the implantable capacitive ion diode.
The molybdenum trioxide-based electrode prepared by the method of the embodiment shows very remarkable ion screening effect in sodium sulfate electrolyte, namely the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated on Na + Low potential region contributing to capacity, whereas SO 4 2- The high potential region contributing to the capacity shows only a very weak electric double layer capacitance. The first type of rectification ratio of the molybdenum trioxide electrode in the sodium sulfate electrolyte is calculated to be 58, the second type of rectification ratio is calculated to be 96.2 percent, and the values are far higher than those of the 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, namely the device can be normally charged and discharged only in forward bias, and the device can hardly store charges in reverse bias. Meanwhile, the capacitive ion diode can efficiently and stably work in a classical logic operation circuit of an AND gate type and an OR gate type, and has good practical application prospect.
Example 4
Firstly, preparing molybdenum trioxide powder material by a hydrothermal method, dispersing the molybdenum trioxide powder material, super-P and polyacrylic acid in deionized water according to a mixture ratio of 7:2:1, uniformly coating the slurry on carbon cloth, and controlling the loading amount of active substances to be 3mg/cm 2 And drying in a vacuum oven and cutting to obtain the working electrode.
Secondly, preparing a counter electrode based on biomass carbon by adopting the same method, and controlling the loading amount of active substances to be 5mg/cm 2 。
Third step, phosphoric acid (H) 3 PO 4 ) The solution was used as an electrolyte at a concentration of 1mol/L. In the electrolyte, H + Can be efficiently stored in molybdenum trioxide material, while PO 4 3- The molybdenum trioxide can show obvious anion-cation screening effect because of steric hindrance and electrostatic repulsion which can not be stored in the molybdenum trioxide material.
And fourthly, assembling the molybdenum trioxide-based working electrode and the biomass carbon-based counter electrode in a lamination mode, injecting phosphoric acid electrolyte into the molybdenum trioxide-based working electrode and the biomass carbon-based counter electrode, and then packaging the whole device by fibroin to obtain the implantable capacitive ion diode.
The molybdenum trioxide electrode prepared by the method of the embodiment shows very remarkable ion screening effect in phosphoric acid electrolyte, namely the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated on H + Low potential region contributing to capacity, while at PO 4 3- The high potential region contributing to the capacity shows only a very weak electric double layer capacitance. The first class of rectification ratio of the molybdenum trioxide electrode in the phosphoric acid electrolyte is calculated to be up to 125, the second class of rectification ratio is calculated to be up to 97.5 percent, and the values are far higher than those of the 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, namely the device can be normally charged and discharged only in forward bias, and the device can hardly store charges in reverse bias. Meanwhile, the capacitive ion diode can efficiently and stably work in a classical logic operation circuit of an AND gate type and an OR gate type, and has good practical application prospect.
Example 5
Firstly, preparing molybdenum trioxide powder material by a hydrothermal method, ultrasonically dispersing the molybdenum trioxide powder material and bacterial cellulose in deionized water according to a mass ratio of 9:1, and directly carrying out suction filtration on the dispersion liquid by a vacuum suction filtration method to form a film and controlling the loading amount of active substances to be 2mg/cm 2 And attaching the film layer on the surface of the conductive substrate, drying in a vacuum oven, and cutting to obtain the working electrode.
Secondly, preparing a counter electrode based on the carbon nano tube by adopting the same method, and controlling the loading amount of the active substance to be 4mg/cm 2 。
And thirdly, a mixed solution of hydrochloric acid (HCl) and potassium chloride (KCl) is selected as an electrolyte, wherein the concentration of the hydrochloric acid is 0.1mol/L, and the concentration of the potassium chloride is 4mol/L. In the electrolyte, H + And K + Two cations can be in molybdenum trioxide materialHigh efficiency storage of Cl - The molybdenum trioxide can show obvious anion-cation screening effect because of steric hindrance and electrostatic repulsion which can not be stored in the molybdenum trioxide material.
And fourthly, assembling the molybdenum trioxide-based working electrode and the carbon nano tube-based counter electrode in a lamination mode, injecting a mixed electrolyte of hydrochloric acid and potassium chloride into the molybdenum trioxide-based working electrode, and then packaging the whole device by Cellulose Acetate (CA) to obtain the implantable capacitance type ion diode.
The molybdenum trioxide electrode prepared by the method of the embodiment shows very remarkable ion screening effect in the mixed electrolyte of hydrochloric acid and potassium chloride, namely the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated on H + And K + Low potential region contributing to capacity, while in Cl - The high potential region contributing to the capacity shows only a very weak electric double layer capacitance. The first class rectification ratio of the molybdenum trioxide electrode in the mixed electrolyte of hydrochloric acid and potassium chloride is up to 108, the second class rectification ratio is up to 97.3 percent, and the values are far higher than those of the 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, namely the device can be normally charged and discharged only in forward bias, and the device can hardly store charges in reverse bias. Meanwhile, the capacitive ion diode can efficiently and stably work in a classical logic operation circuit of an AND gate type and an OR gate type, and has good practical application prospect.
Example 6
Firstly, preparing molybdenum trioxide powder material by a hydrothermal method, dispersing the molybdenum trioxide powder material and Super-P, PTFE mixed materials in ethanol according to a ratio of 7:2:1, uniformly coating the slurry on a graphite 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 working electrode.
Second, a counter electrode based on commercial activated carbon was prepared by the same method as described above, and the active material loading was controlled to 2mg/cm 2 。
Third, sodium chloride (NaCl), potassium chloride (KCl), disodium hydrogen phosphate (Na) 2 HPO 4 ) Potassium dihydrogen phosphate (KH) 2 PO 4 ) Wherein the concentration of sodium chloride is 0.1mol/L, the concentration of potassium chloride is 0.02mol/L, the concentration of disodium hydrogen phosphate is 0.05mol/L, and the concentration of potassium dihydrogen phosphate is 0.01mol/L. In the electrolyte, na + 、K + And H + Three cations can be stored efficiently in the molybdenum trioxide material, while Cl - PO (Point of sale) 4 3- The two anions cannot be stored in the molybdenum trioxide material due to steric hindrance and electrostatic repulsion, so that the molybdenum trioxide can show obvious anion-cation screening effect.
Fourthly, assembling the molybdenum trioxide-based working electrode and the commercial active carbon-based counter electrode in a lamination mode, injecting mixed electrolyte of sodium chloride, potassium chloride, disodium hydrogen phosphate and potassium dihydrogen phosphate into the molybdenum trioxide-based working electrode and the commercial active carbon-based counter electrode, and then packaging the whole device by Polydimethylsiloxane (PDMS) to obtain the implantable capacitance type ion diode.
The molybdenum trioxide electrode prepared by the method of the embodiment shows very remarkable ion screening effect in the mixed electrolyte of sodium chloride, potassium chloride, disodium hydrogen phosphate and monopotassium hydrogen phosphate, namely the charge storage capacity of the molybdenum trioxide electrode is mainly concentrated in Na + 、K + And H + The three cations contribute to the low potential region of capacity, while in Cl - PO (Point of sale) 4 3- The high potential interval of the two anion contributing capacities shows only very weak electric double layer capacitance. The first type rectification ratio of the molybdenum trioxide electrode in the mixed electrolyte of sodium chloride, potassium chloride, disodium hydrogen phosphate and potassium dihydrogen phosphate is calculated to be 127, the second type rectification ratio is calculated to be 97.8%, and the values are far higher than those of the 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, namely the device can be normally charged and discharged only in forward bias, and the device can hardly store charges in reverse bias. Meanwhile, the capacitance type ion diode can be used for conducting the currentThe typical AND gate and OR gate logic operation circuits work efficiently and stably, and have good practical application prospect.
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 of making an implantable capacitive ion diode, comprising:
preparing a molybdenum trioxide-based working electrode and a porous carbon-based counter electrode;
preparing an electrolyte, wherein only one ion type in anions and cations of the electrolyte can be stored in molybdenum trioxide;
and assembling the molybdenum trioxide-based working electrode and the porous carbon-based counter electrode, placing the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode in the electrolyte, and then packaging the assembled molybdenum trioxide-based working electrode and the porous carbon-based counter electrode by utilizing a biocompatible material to obtain the implantable capacitive ion diode.
2. The method of claim 1, wherein the porous carbon-based counter electrode active material is loaded 1 to 10 times the molybdenum trioxide-based working electrode active material.
3. The method of manufacturing an implantable capacitive ion diode according to claim 1, wherein the method of manufacturing a molybdenum trioxide-based working electrode specifically comprises:
mixing molybdenum trioxide powder 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 molybdenum trioxide-based working electrode.
4. The method for preparing an implantable capacitive ion diode according to claim 3, wherein the mass ratio of the molybdenum trioxide powder material, the conductive agent and the binder is 7-9:1-2:1.
5. The method of manufacturing an implantable capacitive ion diode according to claim 1, wherein the step of manufacturing a porous carbon-based counter electrode 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.
6. The method of claim 5, wherein the mass ratio of the porous carbon material, the conductive agent, and the binder is 7-9:1-2:1.
7. The method of claim 3 or 5, wherein the conductive agent comprises one of conductive carbon black, ketjen black, acetylene black, carbon nanotubes, graphene nanoplatelets;
the binder comprises one of polytetrafluoroethylene, sodium carboxymethyl cellulose, polyacrylic acid, polyethylene oxide, sodium alginate and bacterial cellulose;
the dispersing agent comprises one of deionized water, ethanol, ethylene glycol, propylene carbonate and N-methyl pyrrolidone.
8. The method of manufacturing an implantable capacitive ion diode according to claim 1, wherein the electrolyte in the electrolyte solution is an inorganic salt or an inorganic acid;
the concentration of the electrolyte is 0.001-10 mol/L.
9. An implantable capacitive ion diode prepared by the method of preparing an implantable capacitive ion diode according to any one of claims 1-8.
10. A logic circuit using the implantable capacitive ion diode of claim 9.
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