An anti-hydrogen enhancement protection method between the current collector of a transparent energy storage battery and the electrode material

Abstract

The present invention discloses a method for anti-hydrogen enhancement protection between a transparent energy storage battery current collector and an electrode material, which includes first coating an electrode material on a conductive transparent current collector and sintering it at a high temperature to form an electrode material thin film; secondly, preparing an electrolyte solution required for electro-depositing a polymer anti-hydrogen protection layer; then putting the electrolyte solution into a glass electrolytic cell, using the electrode material thin film on the transparent current collector as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel as the reference electrode, scanning 60-80 cycles at a voltage of 0 to +1.5V with a scanning rate of 100mv / s. After the scanning is completed, the working electrode is rinsed with ethanol and cured at 150 degrees Celsius in the air for 30 minutes to obtain a "protection layer + conductive transparent current collector / electrode material" structure. The present invention prepares an electro-polymerized polymer anti-hydrogen protection layer between the conductive transparent current collector and the electrode material through an electrochemical method, constructs a battery with the transparent current collector as the electrode, can conduct a light transmittance experiment on this battery, and expands the application of the transparent current collector.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical energy storage, and particularly to a method for enhancing hydrogen resistance protection between a current collector of a transparent energy storage battery and an electrode material. Background Art

[0002] Aqueous ion batteries have received increasing attention in current research due to their low cost, high safety, and fast ion migration. In traditional aqueous hydrogen ion energy storage batteries, opaque materials such as copper sheets, titanium sheets, and titanium plates are often used as current collectors for coating electrode materials on the working electrode substrate. This makes it impossible to directly observe when detecting and viewing the battery, and other complex technical means are required.

[0003] Directly preparing electrode materials on a transparent conductive current collector by sintering. This "transparent conductive current collector / electrode material" heterogeneous structure is unique and has excellent performance. Its greatest advantage is being nearly transparent in a wide wavelength band, which is not possessed by other commonly used materials in energy storage batteries. At the same time, the preparation process does not require conductive agents and binders, reducing the side reactions brought by them, and does not require complex and expensive equipment, achieving one-step preparation. In aqueous hydrogen ion batteries, acidic electrolytes are widely used, which can provide a large number of hydrogen ions. When an aqueous ion energy storage battery adopts this "transparent conductive current collector / electrode material" heterogeneous structure, due to the corrosive attack of hydrogen ions on the interface between the conductive transparent current collector and the electrode material, the structure and performance fail. Therefore, the "transparent conductive current collector / electrode material" heterogeneous structure cannot be used as an electrode in aqueous hydrogen ion batteries currently. The present invention uses a unique in-situ electroactive triggered polymerization poly(phenylene ether) polymer layer protection technology, which can make the interface between the transparent substrate and the electrode material more stable, inhibit the attack of hydrogen ions, and prepare a high-performance core negative electrode component of a negative electrode material / conductive substrate that is resistant to hydrogen ion impact and peeling, enabling the aqueous transparent energy storage battery to obtain a considerable capacity. Summary of the Invention

[0004] The purpose of the present invention is to solve the technical problems existing in the prior art and provide a method for enhancing hydrogen resistance protection between a current collector of a transparent energy storage battery and an electrode material.

[0005] To achieve the above purpose, the technical solution provided by the present invention is: A method for enhancing hydrogen resistance protection between a current collector of a transparent energy storage battery and an electrode material, which includes the following steps:

[0006] (1) Coating an electrode material on a conductive transparent current collector and sintering at high temperature to form an electrode material film;

[0007] (2) Preparing an electrolyte solution required for electro-depositing a poly(phenylene ether) polymer hydrogen resistance protection layer;

[0008] (3) Place the electrolyte solution in step (2) into a glass electrolytic cell, use the electrode material film on the transparent current collector in step (1) as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel electrode as the reference electrode. Scan 60 - 80 cycles at a scan rate of 100 mv / s under a voltage of 0 to +1.5V. After the scanning is completed, rinse the working electrode with ethanol and cure it at 150 °C in air for 30 minutes to obtain a structure of "electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material".

[0009] Preferably, the conductive transparent current collector used in step (1) is one of F-doped SnO2 conductive glass, F-doped indium tin oxide conductive glass, F-doped aluminum-doped zinc oxide transparent conductive glass, and F-doped flexible polymer conductive film.

[0010] Preferably, the electrolyte in step (2) is a polyphenylene ether electro-polymerized polymer solution.

[0011] Preferably, the structure of "polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material" in step (3) forms a half-cell or a full-cell with the positive electrode material to obtain charge-discharge capacity in an acetic acid acidic solution.

[0012] Advantages of the present invention:

[0013] 1. The present invention obtains an electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer through an electrochemical method, and prepares a high-performance core negative electrode component of a negative electrode material / conductive substrate that is resistant to hydrogen ion impact and peeling, solving the problem that the electrode material is prone to falling off the current collector due to the attack of hydrogen ions in the electrolyte between the conductive transparent current collector and the electrode material in an aqueous ion energy storage battery.

[0014] 2. The present invention prepares an electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer between the conductive transparent current collector and the electrode material through an electrochemical method, constructs a battery with a transparent current collector as the electrode, and can conduct a light transmittance experiment on this battery, and expands the application of the transparent current collector.

[0015] 3. The present invention uses a conductive transparent current collector in an energy storage battery, and optical means can be used for measurement when detecting the internal situation of the battery, solving the problem that the internal condition of the battery electrode cannot be directly observed. Description of the Drawings

[0016] The drawings described herein are used to provide a further understanding of the present invention, form a part of the present invention, and the schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention.

[0017] Figure 1 is a schematic diagram of the aqueous ion battery of the present invention;

[0018] Figure 2 is the transparent electrode of the energy storage battery after obtaining the anti-hydrogen enhanced protective layer by electrochemistry of the present invention;

[0019] Figure 3 is the process of attaching the electrode material on the transparent current collector of the present invention and electrochemically triggering the polymerization of the polymer anti-hydrogen enhanced protective layer on the substrate. Specific Embodiments

[0020] This part will describe in detail the specific embodiments of the present invention. The preferred embodiments of the present invention are shown in the drawings. The role of the drawings is to supplement the description in the text part of the specification, enabling people to intuitively and vividly understand each technical feature and the overall technical solution of the present invention. However, it should not be construed as a limitation on the protection scope of the present invention.

[0021] In the description of the present invention, it should be understood that for the orientation description, such as the orientation or positional relationship indicated by up, down, front, back, left, right, etc., is based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the present invention.

[0022] In the description of the present invention, the meaning of several is one or more, the meaning of multiple is more than two, and the understanding of greater than, less than, exceeding, etc. does not include the present number, and the understanding of above, below, within, etc. includes the present number. If the first and second are described only for the purpose of distinguishing technical features, they should not be construed as indicating or implying relative importance or implicitly indicating the quantity of the indicated technical features or implicitly indicating the sequence relationship of the indicated technical features.

[0023] In the description of the present invention, unless otherwise clearly defined, words such as setting, installing, connecting, etc. should be understood in a broad sense, and those skilled in the art can reasonably determine the specific meaning of the above words in the present invention in combination with the specific content of the technical solution.

[0024] Refer to Figures 1 - 3 , a preferred embodiment of the present invention, an anti-hydrogen enhanced protection method between the transparent current collector and the electrode material of the transparent energy storage battery, which includes the following steps:

[0025] (1) Coating the electrode material on the conductive transparent current collector and sintering at high temperature to form an electrode material thin film;

[0026] (2) Preparing the electrolyte solution required for electro-depositing the poly(phenylene oxide) polymer anti-hydrogen protective layer;

[0027] (3) Place the electrolyte solution in step (2) into a glass electrolytic cell. Use the electrode material film on the transparent current collector in step (1) as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel electrode as the reference electrode. Scan 60 - 80 cycles at a scan rate of 100 mv / s under a voltage of 0 to +1.5 V. After the scanning is completed, rinse the working electrode with ethanol and cure it at 150 °C in air for 30 minutes to obtain a structure of "electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material".

[0028] As a preferred embodiment of the present invention, it may further have the following additional technical features:

[0029] In this embodiment, the conductive transparent current collector used in step (1) is one of F-doped SnO2 conductive glass, F-doped indium tin oxide conductive glass, F-doped Al-doped zinc oxide transparent conductive glass, and F-doped flexible polymer conductive film.

[0030] Specifically, cut the transparent current collector (taking F-doped SnO2 conductive glass as an example) to an appropriate size, ultrasonically clean it, and uniformly coat the electrode material (taking TiO2 as an example) on the surface of the transparent current collector by screen printing. Use a muffle furnace to calcine into a film at high temperature to obtain a structure of "conductive transparent current collector / electrode material".

[0031] In this embodiment, the electrolyte solution in step (2) is a polyphenylene ether electro-polymerized polymer solution.

[0032] Specifically, for the preparation method of the polyphenylene ether electro-polymerized polymer solution electrolyte, take 50 ml of deionized water, 50 ml of ethanol, and 5 ml of 2-butoxyethanol to mix to obtain 105 ml of a mixed solution. Then take 100 ml of the mixed solution and add 0.6 g of phenol, 1.5 g of 2-allylphenol, and 1 g of lithium perchlorate to prepare the polyphenylene ether electro-polymerized polymer solution electrolyte.

[0033] In this embodiment, the structure of "electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material" in step (3) forms a half-cell or a full-cell with the positive electrode material to obtain charge and discharge capacity in an acetic acid acidic solution.

[0034] Example 1

[0035] This embodiment includes the following steps:

[0036] (1) Coat an electrode material on a conductive transparent current collector and sinter it at high temperature into an electrode material film;

[0037] (2) Prepare the electrolyte solution required for electro-depositing a polymer hydrogen-resistant protective layer;

[0038] (3) Cut the transparent current collector (here, F-doped SnO₂ conductive glass is taken as an example) to an appropriate size, wash it ultrasonically, and uniformly coat the electrode material (here, TiO₂ is taken as an example) on the surface of the transparent current collector by screen printing. Then, use a muffle furnace to calcine it into a film at high temperature to obtain a "conductive transparent current collector / electrode material" structure;

[0039] (4) Prepare the electrolyte required for depositing the polymer anti-hydrogen enhanced protective layer. In this embodiment, a polyphenylene oxide electro-polymerized polymer solution electrolyte is selected. The preparation method of the polyphenylene oxide electro-polymerized polymer solution electrolyte is as follows: Take 50 ml of deionized water, 50 ml of ethanol, and 5 ml of 2-butoxyethanol and mix them to obtain 105 ml of a mixed solution. Then, take 100 ml of the mixed solution, add 0.6 g of phenol, 1.5 g of 2-allylphenol, and 1 g of lithium perchlorate to prepare the solution required for the experiment. Add an appropriate amount of 0.01 M tetrabutylammonium hydroxide to adjust the solution required for the experiment to pH = 9;

[0040] (5) Put an appropriate amount of this solution into a glass electrolytic cell. Use the TiO₂ film on the transparent substrate F-doped SnO₂ conductive glass as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel electrode as the reference electrode. Scan at a sweep rate of 100 mv / s at a voltage of 0 to +1.5 V for 60 to 80 cycles;

[0041] (6) After the scanning is completed, rinse the working electrode with ethanol and cure it in air at 150 °C for 30 minutes to obtain an "electro-polymerized polyphenylene oxide polymer anti-hydrogen protective layer + conductive transparent current collector / electrode material" structure;

[0042] (7) Combine it with the positive electrode material to form a half-cell or a full-cell to obtain the charge-discharge capacity in an acetic acid acidic solution.

[0043] The present invention obtains an electro-polymerized polymer anti-hydrogen protective layer by an electrochemical method, and prepares a high-performance core negative electrode component of a negative electrode material / conductive substrate that is resistant to hydrogen ion impact and anti-peeling, solving the problem that the electrode material easily falls off the current collector due to the attack of hydrogen ions in the electrolyte between the conductive transparent current collector and the electrode material in the aqueous ion energy storage battery.

[0044] The present invention prepares an electro-polymerized polyphenylene oxide polymer anti-hydrogen protective layer between the conductive transparent current collector and the electrode material by an electrochemical method, constructs a battery with a transparent current collector as the electrode, and can perform a light transmittance experiment on this battery, and expands the application of the transparent current collector.

[0045] The present invention uses a conductive transparent current collector in the energy storage battery, and can use optical means to measure when detecting the internal situation of the battery, solving the problem that the internal condition of the battery electrode cannot be directly observed.

[0046] On the premise of no conflict, those skilled in the art can freely combine and superimpose the above-mentioned additional technical features.

[0047] The above description is only the preferred implementation mode of the present invention. As long as the technical solutions that achieve the purpose of the present invention by basically the same means fall within the protection scope of the present invention.

Claims

1. A method for anti-hydrogen enhancement protection between the current collector of a transparent energy storage battery and the electrode material, characterized in that: The method comprises the following steps: (1) Coating an electrode material on a conductive transparent current collector and sintering at a high temperature to form an electrode material thin film; (2) Preparing an electrolyte solution required for electro-depositing a polyphenylene ether polymer hydrogen-resistant protective layer; (3) Placing the electrolyte solution in step (2) into a glass electrolytic cell to deposit a polyphenylene ether polymer hydrogen-resistant protective layer, obtaining a structure of "electro-polymerized polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material"; 2. A method for anti-hydrogen enhancement protection between a current collector of a transparent energy storage battery and an electrode material according to claim 1, characterized in that: The structure of "polyphenylene ether polymer hydrogen-resistant protective layer + conductive transparent current collector / electrode material" and a positive electrode material form a half-cell or a full cell, and a charge-discharge capacity is obtained in an acetic acid acidic solution.

Images