CN116759519A - Zinc cathode with micro-channels and preparation method and application thereof - Google Patents

Zinc cathode with micro-channels and preparation method and application thereof Download PDF

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Publication number
CN116759519A
CN116759519A CN202310309503.6A CN202310309503A CN116759519A CN 116759519 A CN116759519 A CN 116759519A CN 202310309503 A CN202310309503 A CN 202310309503A CN 116759519 A CN116759519 A CN 116759519A
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China
Prior art keywords
zinc
micro
dimensional
conductive layer
channels
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CN202310309503.6A
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Chinese (zh)
Inventor
官操
马菲
曹庆贺
高勇
张海峰
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Ningbo Research Institute of Northwestern Polytechnical University
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Ningbo Research Institute of Northwestern Polytechnical University
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Priority to CN202310309503.6A priority Critical patent/CN116759519A/en
Publication of CN116759519A publication Critical patent/CN116759519A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes

Abstract

The invention discloses a zinc cathode with a micro-channel, a preparation method and application thereof, and belongs to the field of metal battery materials. The zinc cathode with the micro-channels provided by the invention can effectively optimize electric field distribution and Zn 2+ Ion flux and local current density, thereby realizing ideal deposition behavior of metal zinc from bottom to top, and having high stability, simple preparation process and low costIs suitable for mass production.

Description

Zinc cathode with micro-channels and preparation method and application thereof
Technical Field
The invention relates to the field of metal battery materials, in particular to a zinc anode with a micro-channel, and a preparation method and application thereof.
Background
In the last decades, although lithium ion batteries have been developed dramatically, the scarcity of metal resources, the high price and high safety risks have greatly limited their use in the future. Rechargeable Aqueous Zinc Ion Batteries (AZIBs) are widely regarded as a promising reliable alternative due to the various advantages of high safety of zinc cathodes, abundant natural resources, high theoretical capacity and the like.
However, the zinc anode of the aqueous zinc ion battery has problems of poor plating/stripping reversibility and dendrite growth, so that the cycle stability thereof is not ideal, and in addition, the zinc anode also faces problems of side reactions and corrosion in the aqueous electrolyte. These problems can greatly reduce Coulombic Efficiency (CE) and capacity, and can easily form sharp dendrites, leading to battery failure.
In order to solve the above problems, an effective method is to construct an artificial protective layer. Reportedly, such as ZnS, znF 2 Materials such as Sn, PVB and MXene can effectively inhibit side reactions and improve stability. However, when the local electric field becomes large and the electrode surface is bumped, rapid growth of dendrites (hot spot effect) can still be observed. Especially at high currents/capacities, so they only work well at low currents/capacities. Constructing a three-dimensional zinc anode is another promising method of stabilizing zinc anodes. The three-dimensional structure can effectively increase the specific surface area to obtain more reaction sites and reduce the local electric field intensity to achieve uniform zinc deposition. For example, chen et al prepared an agnps@cc electrode by using commercial carbon cloth as a three-dimensional scaffold, which achieved good zinc deposition behavior and long cycling stability. The patent discloses a three-dimensional nickel-zinc electrode with a multichannel lattice structure and a super-hydrophilic surface, which effectively improves the electric field distribution and induces uniform deposition of zinc. In another work, a three-dimensional zinc anode with micropores was constructed using an ITO template, which also achieved good spatially selective deposition of zinc. The design of the three-dimensional zinc anode with the gradient structure can effectively promote local electricityCharge transport kinetics and optimizes the zinc deposition process. For example, the sinker et al prepared a three-dimensional gradient zinc anode with Cu foam at the bottom, ni foam in the middle, and NiO coating on top, which resulted in Zn/Zn 2+ The reaction resistance increases gradually from bottom to top. The gradient zinc cathode effectively avoids growth of dendrite on the top surface and is at 3mA cm -2 The lower panel shows a 250 hour steady cycle. However, because the gradient electrode uses metal foam as a scaffold, the trans-scale variation of the structure and non-uniform micro/nanopores may disturb Zn 2+ Diffusion of ions and slow down charge transfer. In addition, the final zinc anode requires a further zinc deposition process, which not only complicates the electrode preparation process, but also the inactive foam takes up much weight, sacrificing energy density.
Therefore, developing a new zinc negative electrode gradient design strategy has very important practical significance, can well control zinc deposition and inhibit side reactions, and finally obtains stable cycle performance under high current/capacity.
Disclosure of Invention
The invention aims to solve the problem of stabilizing and recycling the cathode of a battery under the high-current and high-capacity application environment.
To solve the above problems, the first aspect of the present invention provides a zinc anode with a microchannel, the zinc anode comprising a dual gradient electrode, the dual gradient electrode comprising a hydrophilic conductive layer and a hydrophobic insulating layer, the hydrophilic conductive layer being located at the bottom of a three-dimensional microchannel pattern, the hydrophobic insulating layer being covered on top of the three-dimensional microchannel pattern. The hydrophobic insulating layer can increase the interfacial free energy between the zinc substrate and the electrolyte, and the hydrophilic conductive layer aids in redox and electrolyte penetration. Both of which help to inhibit side reactions of metallic zinc with the water electrolyte. At the same time, the hydrophobic insulating layer prevents zinc deposition on the top surface, while the bottom hydrophilic conductive layer more readily initiates electron-ion exchange. The gradient conductivity effectively induces the electric field distribution, the zinc ion flux and the local current density to move towards the bottom of the micro-channel, so that the ideal deposition behavior of the metal zinc from bottom to top is realized; in addition, the hydrophilic conductive layer can make the nucleation and deposition process of zinc uniform and further inhibit the growth of dendrites, so that the zinc anode with the micro-channels provided by the invention can show good electrochemical characteristics.
Preferably, the three-dimensional microchannel pattern ensures that metallic zinc is deposited from bottom to top, the hydrophobic insulating layer prevents zinc from depositing on the top surface, the hydrophilic conductive layer can induce electron-ion exchange, and the dual gradient structure can effectively induce electric field distribution, zn 2+ The ion flux and the local current density move towards the bottom of the micro-channel, thereby realizing ideal deposition behavior of the metal zinc from bottom to top.
Preferably, the material of the hydrophilic conductive layer is selected from any one of copper, silver, bismuth, tin and gold.
Preferably, the raw material of the hydrophobic insulating layer is selected from any one of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polyvinyl chloride and poly perfluoroethylene propylene.
Further, a second aspect of the present invention provides a method for preparing the aforementioned zinc anode with micro-channels, comprising the steps of:
s1: generating a hydrophilic conductive layer on the surface of the zinc foil;
s2: embossing a three-dimensional microchannel pattern on the zinc foil of the hydrophilic conductive layer;
s3: and generating a hydrophobic insulating layer on the three-dimensional microchannel pattern to obtain the zinc cathode with the microchannel. The bare zinc foil can generate serious corrosion and side reaction in electrolyte, and deposited zinc is uneven, so zinc dendrites are easy to form, the cycle performance is poor, and the zinc cathode provided by the invention can better reduce the local electric field intensity.
Preferably, in the step S1, the hydrophilic conductive layer is prepared by a substitution method.
Preferably, in the step S2, the three-dimensional micro-channel pattern is prepared by using a mold for imprinting.
Preferably, in the step S2, the preparation method of the three-dimensional micro-channel pattern includes: and (3) imprinting the die with the three-dimensional micro-channels on the zinc foil of the hydrophilic conductive layer to obtain the three-dimensional micro-channel pattern.
Further, a third aspect of the invention provides a battery comprising the zinc anode with microchannels as described above.
Compared with the traditional battery, the battery with the micro-channel provided by the invention has better stability.
The invention has the beneficial effects that: the zinc cathode with the micro-channel provided by the invention has the double gradient electrodes, so that the three-dimensional micro-channel forms a gradient micro-channel, and the electric field distribution and Zn are effectively optimized 2+ Ion flux and local current density, thereby achieving the ideal bottom-up deposition behavior of metallic zinc. Not only is controllable and uniform zinc deposition realized, but also short circuit possibly caused by top dendrite growth is prevented, thereby obtaining a zinc battery cathode with high stability; the present invention does not involve high temperature or complicated post-treatment during the whole preparation process, and the mold for imprinting the three-dimensional microchannel pattern can be simply reused, which effectively simplifies the manufacturing process and reduces the cost. The preparation method is convenient and efficient, and is suitable for large-scale production; the battery provided by the invention has the double-gradient negative electrode of the three-dimensional microchannel, and has the advantages of high stability, high capacity, strong recycling performance and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a zinc anode with a micro-channel prepared in example 1 of the present invention;
FIG. 2 shows the PVDF-Sn@Zn gradient electrode of example 2 of the invention at 15mAh cm -2 Scanning electron microscope pictures after capacity deposition of Zn;
FIG. 3 is a graph showing the cycle performance test of the symmetrical batteries prepared in example 2 and comparative example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of a zinc cathode of the symmetric battery prepared in example 2 of the present invention after 100 charge-discharge cycles;
fig. 5 is a cycle performance test chart of the full cell manufactured in example 3 and comparative example 2 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It should be noted that the following examples are only for illustrating the implementation method and typical parameters of the present invention, and are not intended to limit the scope of the parameters described in the present invention, so that reasonable variations are introduced and still fall within the scope of the claims of the present invention.
It should be noted that endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and that such range or value should be understood to include values approaching such range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described in the background, the existing zinc cathode has the defects of non-ideal circulation effect, easy formation of sharp dendrites, failure of a battery and the like, and the specific embodiment of the invention provides a zinc cathode with a microchannel, and a preparation method and application thereof. The zinc cathode with the micro-channels comprises a double-gradient structure which is specifically divided into three layers, wherein the double-gradient structure comprises a hydrophilic conductive layer, a hydrophobic insulating layer and a three-dimensional micro-channel pattern positioned between the hydrophilic conductive layer and the hydrophobic insulating layer.
In the above embodiment, the hydrophobic insulating layer is selected from any one of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polyvinyl chloride, and polyperfluoroethylene propylene.
In the above embodiment, the three-dimensional micro-channel pattern may be obtained by imprinting the hydrophilic conductive layer using a related mold.
In addition to the above embodiments, the present invention further provides two applications of the foregoing zinc anode with micro-channels, and the foregoing zinc anode with micro-channels is applied to a symmetrical battery and a full battery, respectively. The symmetrical battery and the full battery containing the zinc cathode with the micro-channels provided by the specific embodiment of the invention can keep good zinc coating/stripping reversibility and have good cycle performance.
Example 1
The embodiment provides a preparation method of a zinc anode with a micro-channel. First, the pre-cleaned zinc foil was covered with an insulating Kapton film to ensure that the reaction was only carried out on one side. The treated zinc foil was then placed in 0.4M SnCl 4 In solution and reacted for 5 minutes. Finally, the Sn@Zn electrode is obtained after drying.
Subsequently, the obtained zinc foil of Sn@Zn electrode was pressed together with a pre-cleaned stainless steel mesh (SSM, 500 mesh) by mechanical rolling to form a three-dimensional micro-channel pattern, and a SSM-imprinted battery negative electrode (Sn@Zn-SSM) was obtained.
Subsequently, 200 mg of PVDF was added to 2 ml of N-methyl-2-pyrrolidine (NMP) to form a homogeneous PVDF solution, which was spin-coated (4000 rpm, 1 min) onto the three-dimensional microchannel pattern of Sn@Zn-SSM electrode to give the final PVDF-Sn@Zn gradient electrode.
From the Scanning Electron Microscope (SEM) image of fig. 1, the PVDF-sn@zn electrode exhibited good flatness, the portion imprinted by SSM formed micro-channels and uniformly coated with Sn layer, while the other areas not imprinted were covered by PVDF, thus forming a unique dual gradient electrode with micro-channels.
Example 2
The embodiment provides a preparation method of a zinc ion symmetrical battery. And assembling the prepared battery cathode and electrolyte into a zinc ion symmetrical battery, wherein the electrolyte is 2M zinc sulfate solution (PVDF-Sn@Zn// PVDF-Sn@Zn).
To study the deposition behavior of gradient electrode zinc, FIG. 2 shows that PVDF-Sn@Zn gradient electrode is deposited at 15 mAh.cm -2 Scanning electron microscope image after volume deposition of Zn. After depositing zinc, it was observed that zinc was mostly deposited at the bottom of the microchannel, and no significant deposition occurred on the PVDF layer of the top layer, indicating that the microchannel gradient design preferentially induced zinc nucleation and growth at the bottom of the microchannel. And a uniform and flat surface can be observed, without observationBy non-uniform protrusions, it was shown that the microchannel gradient design effectively reduced dendrites, promoting stable cycling at high current densities/capacities.
Comparative example 1
A symmetric battery (Zn foil// Zn foil) was assembled using zinc foil as the negative electrode of the battery and a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate as the electrolyte.
The cycle performance of the symmetrical cells of example 2 and comparative example 1 was tested and the results are shown in FIG. 3, where PVDF-Sn@Zn// PVDF-Sn@Zn cells were measured at 5mA cm -2 /5mAh cm -2 Is maintained for 150 hours at a high current density/capacity. In contrast, zn foil// Zn foil cells only short out after 45 hours (dendrites puncture the separator, resulting in cell failure). The microchannel gradient electrode of example 2 was shown to be at 5mA cm -2 Exhibits good cycling stability at high current densities.
The morphology of the PVDF-sn@zn gradient electrode of the symmetric cell prepared in example 2 after charge-discharge cycles was further studied, and the results are shown in fig. 4. It was found that the PVDF-sn@zn gradient electrode maintained good Zn plating/stripping reversibility during repeated charge and discharge and no significant dendrites were observed after 100 cycles.
Example 3
And assembling the prepared battery cathode, the battery anode and the electrolyte into a zinc ion full battery, wherein the battery anode is a vertical graphene nano sheet with manganese dioxide grown on the surface, and the electrolyte is a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate.
Comparative example 2
A full cell (MnO) is assembled by taking zinc foil as a cell cathode, taking manganese dioxide as a cell anode, taking a mixed solution of 2M zinc sulfate and 0.1M manganese sulfate as an electrolyte, and growing manganese dioxide in situ on carbon cloth decorated by vertical graphene 2 @C//PVDF-Sn@Zn)。
The cycling performance of the zinc ion full cells of example 3 and comparative example 2 was tested, and the results are shown in fig. 5, wherein the zinc ion cell of example 3 still maintains 93.4% of the initial capacity after 250 cycles, while the zinc ion cell of comparative example 2 has a short circuit after 160 cycles, further demonstrating that the zinc ion cell of example 3 has good negative electrode stability, and demonstrating the advantages of the microchannel gradient design.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.

Claims (9)

1. The zinc cathode with the micro-channels is characterized by comprising a dual-gradient electrode, wherein the dual-gradient electrode comprises a hydrophilic conductive layer and a hydrophobic insulating layer, the hydrophilic conductive layer is positioned at the bottom of the three-dimensional micro-channel pattern, and the hydrophobic insulating layer covers the top of the three-dimensional micro-channel pattern.
2. The zinc anode with micro-channels according to claim 1, wherein the three-dimensional micro-channel pattern is arranged in an array.
3. The zinc anode with micro-channels according to claim 1, wherein the hydrophilic conductive layer is made of any one of copper, silver, bismuth, tin and gold.
4. The zinc anode with micro-channel according to claim 1, wherein the raw material of the hydrophobic insulating layer is selected from any one of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polyvinyl chloride, and poly perfluoroethylene propylene.
5. A method for preparing a zinc anode with a microchannel according to any one of claims 1 to 4, comprising the steps of:
s1: generating a hydrophilic conductive layer on the surface of the zinc foil;
s2: embossing a three-dimensional microchannel pattern on the zinc foil of the hydrophilic conductive layer;
s3: and generating a hydrophobic insulating layer on the three-dimensional microchannel pattern to obtain the zinc cathode with the microchannel.
6. The method for preparing a zinc anode with micro-channels according to claim 5, wherein in the step S1, the hydrophilic conductive layer is prepared by a substitution method.
7. The method for preparing a zinc anode with micro-channels according to claim 5, wherein in the step S2, the three-dimensional micro-channel pattern is prepared by using a mold imprinting.
8. The method for preparing a zinc anode with micro-channels according to claim 5, wherein in the step S2, the method for preparing a three-dimensional micro-channel pattern comprises the following steps: and (3) imprinting the die with the three-dimensional micro-channels on the zinc foil of the hydrophilic conductive layer to obtain the three-dimensional micro-channel pattern.
9. A battery comprising a zinc anode with microchannels according to any one of claims 1 to 4.
CN202310309503.6A 2023-03-28 2023-03-28 Zinc cathode with micro-channels and preparation method and application thereof Pending CN116759519A (en)

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CN202310309503.6A CN116759519A (en) 2023-03-28 2023-03-28 Zinc cathode with micro-channels and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310309503.6A CN116759519A (en) 2023-03-28 2023-03-28 Zinc cathode with micro-channels and preparation method and application thereof

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CN116759519A true CN116759519A (en) 2023-09-15

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