CN114597080A - Electrochemical capacitor tantalum shell ruthenium dioxide film electrode and preparation method thereof - Google Patents

Electrochemical capacitor tantalum shell ruthenium dioxide film electrode and preparation method thereof Download PDF

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Publication number
CN114597080A
CN114597080A CN202210264433.2A CN202210264433A CN114597080A CN 114597080 A CN114597080 A CN 114597080A CN 202210264433 A CN202210264433 A CN 202210264433A CN 114597080 A CN114597080 A CN 114597080A
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tantalum shell
film electrode
thin film
tantalum
shell
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李祥
雷信顺
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Guizhou Boshili Technology Co ltd
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Guizhou Boshili Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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

Abstract

The invention relates to a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor and a preparation method thereof, belonging to the technical field of thin film electrode preparation. The preparation method of the electrochemical capacitor tantalum shell ruthenium dioxide film electrode comprises the steps of modifying a tantalum shell inner wall substrate by sand blasting, mixed acid corrosion and vacuum plasma in sequence; further adopting a combined process of spin coating and high-frequency heating to uniformly deposit the precursor sol on the inner wall surface of the tantalum shell, and finally adopting a thermal decomposition method to make the precursor sol generate phase change to generate uniform RuO2Thin film active layer to obtain tantalum shell RuO2And a thin film electrode. The thickness of the active layer of the thin film electrode is 9-10 mu m, the adhesive force is more than 12MPa, and the specific capacitance value is 350Fg‑1The number of cycles of charge and discharge is 50000 or more. Therefore, the process can not only increase the tantalum shell thicknessThe electric capacity of the membrane electrode can also improve the stability of the energy storage device in cyclic charge and discharge.

Description

Electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode and preparation method thereof
Technical Field
The invention relates to the technical field of thin film electrode preparation, in particular to a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor and a preparation method thereof.
Background
Electrodes, particularly the cathode, which are key components of tantalum-can electrochemical capacitors, determine the capacitive properties of the energy storage device.
Compared with the laminated electrochemical capacitor energy storage device, the tantalum shell electrochemical capacitor takes the inner wall of the tantalum shell as an electrode substrate and grows ruthenium dioxide (RuO) on the surface of the inner wall2) The active layer is as the negative pole, and tantalum shell plays the encapsulation function effect at energy storage components and parts simultaneously, therefore this energy storage components and parts have advantages such as small, high power density, packaging structure are simple and the cost is lower.
Tantalum shell RuO2The film electrode is mainly applied to pulse main and auxiliary power supply energy storage components in the fields of national defense, military industry and aerospace, so that the film electrode is required to have higher capacitance and excellent cyclic charge and discharge stability in electrochemical performance.
Current tantalum hull RuO2The preparation process of the thin film electrode active layer has certain defects on phase structure and tissue morphology, namely RuO2The phase structure of the film active matter is mainly embodied as a crystal structure, and the capacitance is lower; simultaneously growing RuO on inner wall of tantalum shell2The thickness of the active layer of the film is less uniform, which affects RuO2The adhesive force between the thin film active layer and the inner wall of the tantalum shell increases the internal resistance and reduces the stability of the tantalum shell thin film electrode during the cyclic charge and discharge.
Therefore, how to prepare the tantalum shell film electrode with excellent performance becomes a technical problem to be solved urgently in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor and a preparation method thereof.
In order to achieve the purpose, the invention provides the following scheme:
a preparation method of a tantalum shell ruthenium dioxide thin-film electrode of an electrochemical capacitor comprises the following steps:
corroding the inner wall of the tantalum shell by adopting mixed acid with preset concentration;
ultrasonically cleaning the corroded inner wall of the tantalum shell for multiple times by using deionized water, and then drying;
modifying the inner wall of the tantalum shell after drying treatment by adopting vacuum plasma equipment;
adhering the precursor sol to the inner wall of the modified tantalum shell by adopting a spin coating method and a high-frequency induction drying process;
and placing the coated inner wall of the tantalum shell in a blast heating furnace, and heating at a preset temperature for a preset time to obtain the tantalum shell ruthenium dioxide film electrode.
Preferably, before the mixed acid with the preset concentration is used for corroding the inner wall of the tantalum shell, the method further comprises the following steps:
and (3) treating the surface of the inner wall of the tantalum shell by adopting a sand blasting process.
Preferably, the tantalum content in the tantalum shell is 99.95% or more.
Preferably, the roughness of the inner wall surface of the tantalum shell after being treated by the sand blasting process is between 180 and 200 meshes.
Preferably, the mixed acid comprises 98% concentrated sulfuric acid, 69% concentrated nitric acid, and 40% concentrated hydrofluoric acid; the volume ratio between sulfuric acid with a concentration of 98%, nitric acid with a concentration of 69% and hydrofluoric acid with a concentration of 40% is 4: 2: 1.
preferably, the precursor sol is RuCl3·xH2O is dissolved in n-propanol to form a sol.
Preferably, the preset temperature is 240-260 ℃; the preset time is 2h-3 h.
The electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode provided by the invention is prepared by adopting the preparation method of the electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention provides a preparation method of a ruthenium dioxide film electrode of a tantalum shell of an electrochemical capacitor, which is characterized in that a substrate of the inner wall of the tantalum shell is modified by adopting mixed acid corrosion and vacuum plasma in sequence; further adopting a combined process of spin coating and high-frequency induction heating to enable the precursor sol to be uniformly deposited on the inner wall surface of the tantalum shell, and finally adopting a thermal decomposition method to enable the precursor sol to generate phase change to generate uniform RuO2Thin film active layer to obtain tantalum shell RuO2And a thin film electrode. The thickness of the thin film electrode active layer is 9-10 μm and the adhesive force is more than 12MPa,specific capacitance value of 350Fg-1The number of cycles of charge and discharge is 50000 or more. Therefore, the capacitance of the tantalum shell film electrode can be increased by adopting the process, and the cyclic charge-discharge stability of the energy storage device can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor and a preparation method thereof, which can not only increase the capacitance of the tantalum shell thin film electrode, but also improve the cyclic charge-discharge stability of an energy storage device.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
As shown in fig. 1, the method for preparing a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor provided by the invention comprises the following steps:
step 100: and corroding the inner wall of the tantalum shell by adopting mixed acid with preset concentration. For example, a mixed solution of 98% sulfuric acid, 69% nitric acid and 40% hydrofluoric acid may be used as the mixed acid to etch the inner wall of the tantalum shell. Wherein the volume ratio of the sulfuric acid with the concentration of 98 percent, the nitric acid with the concentration of 69 percent and the hydrofluoric acid with the concentration of 40 percent is 4: 2: 1. and the content of tantalum in the selected tantalum shell is preferably more than 99.95%.
Step 101: and ultrasonically cleaning the corroded inner wall of the tantalum shell for multiple times by using deionized water, and then drying. The step 100 and the step 101 are performed, so that the adhesive force between the thin film active layer and the inner wall of the tantalum shell is increased, and the specific capacitance and the cyclic charge and discharge stability of the thin film electrode of the tantalum shell are improved finally. Wherein, the mixed acid is adopted to corrode the inner wall of the tantalum shell, which is beneficial to improving the surface interface of the inner wall.
Step 102: and modifying the inner wall of the tantalum shell after drying treatment by adopting vacuum plasma equipment. So as to obtain an ultra-clean electrode substrate.
Step 103: and adhering the precursor sol to the inner wall of the modified tantalum shell by adopting a spin coating method and a high-frequency induction drying process. For example, the spin coating apparatus employed is configured as a coaxial rotating triangular fixture to hold the tantalum shell and to accommodate a range of different tantalum shell sizes. During coating, a speed regulating motor is adopted to drive a triangular clamp to rotate the tantalum shell, then the aerosol is coated on the inner wall of the tantalum shell by adopting a mist nozzle, and then the tantalum coating shell is stretched into a high-frequency induction coil to be dried to form a coating film. Also, the precursor sol employed may be RuCl3·xH2O is dissolved in n-propanol to form a sol. Wherein, the sol is dried by an induction coil, the drying time is 2-3s, and the current value is 4-5A.
Step 104: and placing the coated inner wall of the tantalum shell in a blast heating furnace, and heating at a preset temperature for a preset time to obtain the tantalum shell ruthenium dioxide film electrode. For example, the preset temperature is 240-260 ℃, the preset time is 2-3h, and the higher water content in the n-propanol can be fully utilized. Wherein RuO2The thickness of the active layer is 8-10 μm, the phase structure of the film is mainly kept in an amorphous hydrated state, the adhesion between the active layer and the inner wall of the tantalum shell is improved, the value is more than 12MPa, and the specific capacitance value of the tantalum shell film electrode is 350Fg-1The number of the cyclic charge and discharge is more than 50000, and the energy storage component is assembled with the anode cellThe cyclic charge and discharge performance is stable.
Furthermore, in order to enlarge the inner wall surface of the tantalum shell, the inner wall surface of the tantalum shell is treated by adopting a sand blasting process so as to keep the roughness of the inner wall surface interface of 180-200 meshes.
The preparation method of the electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode integrates the advantages of vacuum plasma modification, a spin coating method and a high-frequency induction heating process, and breaks through the RuO of the tantalum shell of the electrochemical capacitor at present2The preparation process of the thin film electrode has limitations, the capacitance and the cyclic charge-discharge stability of the thin film electrode are improved, and the cost is reduced.
The following describes the implementation process and effect of the above method for manufacturing a tantalum shell ruthenium dioxide thin film electrode for an electrochemical capacitor, by using an embodiment, specifically as follows:
(1) the tantalum shell with the purity of 99.95 wt% and a certain size specification is selected as a current collector of the film electrode.
(2) And (3) polishing the inner wall of the tantalum shell by adopting a sand blasting process to enable the roughness of the inner wall to be 180-mesh and 200-mesh, corroding the inner wall of the tantalum shell by adopting a mixed acid solution for 2-3 min, and finally ultrasonically cleaning by adopting deionized water.
(3) And placing the treated tantalum shell in a vacuum plasma equipment cavity, vacuumizing to 0.8-1.0 Pa, and then cleaning the inner wall of the tantalum shell by using a plasma beam for 5-6 min.
(4) RuCl with the concentration of 0.1mol/L is prepared3·xH2O n-propanol coats the sol.
(5) Precursor RuCl adopting mechanical rotation and high-frequency heating combined device3·xH2And the O sol is uniformly coated on the inner wall of the modified tantalum shell. During coating, the tantalum shell is fixed on a tool fixture, then a motor is started to drive the fixture and the tantalum shell to rotate at the same time, the rotating speed is 80-100/min, and then RuCl containing 0.1mol/L3·xH2Spraying O-propanol coating sol on the inner wall of the tantalum shell, making the average thickness of the coating layer about 0.1mm, placing the tantalum shell in an induction coil of a high-frequency heating device, baking the coating film for 4-5 times at a high-frequency induction current value of 4-5A for 2-3s, and co-spinning the coating film layer for 4-5 times.
(6) And (3) placing the coated tantalum shell in a blast furnace at the temperature of 240-260 ℃ for heating for 2-3h, cooling to room temperature along with the furnace, and discharging to obtain the ruthenium dioxide film electrode of the tantalum shell of the electrochemical capacitor.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The principle and the embodiment of the present invention are explained by applying specific examples, and the above description of the embodiments is only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.

Claims (8)

1. A preparation method of a tantalum shell ruthenium dioxide thin film electrode of an electrochemical capacitor is characterized by comprising the following steps:
corroding the inner wall of the tantalum shell by adopting mixed acid with preset concentration;
ultrasonically cleaning the corroded inner wall of the tantalum shell for multiple times by using deionized water, and then drying;
modifying the inner wall of the tantalum shell after drying treatment by adopting vacuum plasma equipment;
adhering the precursor sol to the inner wall of the modified tantalum shell by adopting a spin coating method and a high-frequency induction drying process;
and placing the coated inner wall of the tantalum shell in a blast heating furnace, and heating at a preset temperature for a preset time to obtain the tantalum shell ruthenium dioxide film electrode.
2. The method for preparing the tantalum shell ruthenium dioxide thin film electrode of the electrochemical capacitor according to claim 1, wherein before the mixed acid with the preset concentration is adopted to corrode the inner wall of the tantalum shell, the method further comprises the following steps:
and (3) treating the surface of the inner wall of the tantalum shell by adopting a sand blasting process.
3. The method for preparing the tantalum shell ruthenium dioxide thin film electrode of the electrochemical capacitor as claimed in claim 1, wherein the tantalum content in the tantalum shell is more than 99.95%.
4. The method as claimed in claim 2, wherein the roughness of the inner wall surface of the tantalum shell is 180-200 meshes after sand blasting.
5. The method for preparing the tantalum shell ruthenium dioxide thin film electrode for the electrochemical capacitor as claimed in claim 1, wherein the mixed acid comprises sulfuric acid with a concentration of 98%, nitric acid with a concentration of 69% and hydrofluoric acid with a concentration of 40%; the volume ratio between sulfuric acid with a concentration of 98%, nitric acid with a concentration of 69% and hydrofluoric acid with a concentration of 40% is 4: 2: 1.
6. the method for preparing the tantalum shell ruthenium dioxide thin film electrode of the electrochemical capacitor as claimed in claim 1, wherein the precursor sol is RuCl3·xH2O is dissolved in n-propanol to form a sol.
7. The method for preparing the tantalum shell ruthenium dioxide thin film electrode of the electrochemical capacitor as claimed in claim 1, wherein the preset temperature is 240-260 ℃; the preset time is 2-3 h.
8. The electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode is characterized by being prepared by the method for preparing the electrochemical capacitor tantalum shell ruthenium dioxide thin film electrode according to any one of claims 1 to 7.
CN202210264433.2A 2022-03-17 2022-03-17 Electrochemical capacitor tantalum shell ruthenium dioxide film electrode and preparation method thereof Pending CN114597080A (en)

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CN114597080A true CN114597080A (en) 2022-06-07

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