CN116344730A - Water-based zinc ion battery cathode with surface covered with interface protection layer and preparation method thereof - Google Patents

Water-based zinc ion battery cathode with surface covered with interface protection layer and preparation method thereof Download PDF

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CN116344730A
CN116344730A CN202310192404.4A CN202310192404A CN116344730A CN 116344730 A CN116344730 A CN 116344730A CN 202310192404 A CN202310192404 A CN 202310192404A CN 116344730 A CN116344730 A CN 116344730A
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zinc
lysozyme
silk fibroin
ion battery
solution
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邵正中
周斌
苗变梁
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Fudan University
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Fudan University
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
    • C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
    • C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2462—Lysozyme (3.2.1.17)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01017—Lysozyme (3.2.1.17)
    • 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
    • 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
    • H01M4/628—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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

Abstract

The invention relates to a water-based zinc ion battery anode with an interface protection layer covered on the surface and a preparation method thereof. After the zinc cathode is placed on the surface of a mixed solution of silk fibroin and lysozyme or in the solution for incubation for a period of time, a silk fibroin/lysozyme protein nano film is formed on the surface of the zinc cathode in situ, and the silk fibroin/lysozyme protein nano film is an interface protection layer covering the surface of the zinc cathode. The protective layer in the invention is lysozyme-induced silk fibroin molecule self-assembly, and a compact and uniform negative protective layer is formed in situ at a negative electrode interface. And a large number of polar groups in protein molecules in the interface layer are utilized to regulate and control uniform deposition of negative zinc ions, so that dendrite growth and passivation of the negative interface layer are effectively relieved. In addition, the invention can improve the cycle stability of the water-based zinc ion battery, and the battery of the water-based zinc ion battery cathode with the surface covered with the interface protection layer has very stable cycle performance and also shows excellent rate performance after being cycled under different rates.

Description

Water-based zinc ion battery cathode with surface covered with interface protection layer and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a water-based zinc ion battery anode with an interface protection layer covered on the surface and a preparation method thereof.
Background
The metal zinc has the advantages of low price, abundant reserves, low toxicity, high safety, high energy density, high hydrogen evolution overpotential and the like, and has wide application prospect in the fields of large-scale energy storage, wearable products and the like.
However, the zinc metal negative electrode adopted by the water-based zinc ion battery has the dynamic problem of non-uniform deposition/dissolution of zinc ions on the negative electrode, which can cause non-uniform distribution of a local electric field on one side of the zinc negative electrode, and lead to formation and growth of zinc dendrites, so that the separator is pierced to cause short circuit of the battery. In addition, the presence of a large amount of free water and dissolved oxygen molecules in the aqueous electrolyte causes electrochemical side reactions and uncontrollable solid-liquid interface reactions on the surface of the zinc anode, thereby causing passivation of the zinc anode and loss of anode active material and increasing the risk of corrosion of the zinc anode. The problems of the zinc cathode can lead to the reduction of coulomb efficiency and the excessively rapid capacity decay of the water-based zinc ion battery in the charge and discharge process, thereby greatly influencing the rate performance and the cycle stability of the battery, and severely restricting the development and the commercial application of the water-based zinc ion battery.
In order to solve the problems of negative pole dendrite growth, side reaction corrosion, passivation and the like, researchers have conducted a great deal of research work, and mainly comprise three strategies of zinc negative pole surface modification, current collector design and electrolyte optimization. The local current density is reduced and dendrite growth is limited by designing a proper three-dimensional current collector, so that the cathode cycle stability is improved. However, the optimization of the electrolyte and the improvement of the current collector still have the rapid growth of the negative dendrite under the high current density in the long-term circulation process, so that the problem of unstable negative circulation is difficult to fundamentally solve. The negative electrode surface modification is mainly to control zinc ion deposition, inorganic matter control ion nucleation and metal oxide coating control negative electrode charge distribution through polymer modification so as to relieve the problem of negative electrode dendrite growth. However, the surface protective layer of a polymer or an inorganic substance cannot be modified at an irregular interface to obtain a dense and uniform protective layer, and thus there is a limit to the structure of the negative electrode protective layer. In addition, the traditional organic polymer used as the negative electrode surface modification coating has higher preparation cost, has potential safety hazards of inflammability, toxicity, environmental pollution and the like, and limits the practical application of the organic polymer in the field of large-scale energy storage.
Therefore, the design of a new zinc battery negative electrode protection layer is of great importance for improvement. Therefore, development of a green and environment-friendly water-based zinc ion battery negative electrode protection layer becomes one of the current research hotspots.
Disclosure of Invention
Based on the problem of poor cycle life and cycle stability of a zinc ion battery cathode in the prior art, the invention provides a water-based zinc ion battery cathode with an interface protection layer covered on the surface and a preparation method thereof.
The scheme provided by the invention can effectively regulate and control the deposition behavior of zinc ions in the interface layer of the negative electrode, inhibit the occurrence of side reactions on the surface of the negative electrode, effectively improve the cycle performance and coulomb efficiency of the water-based zinc ion battery, and greatly improve the safety of the water-based zinc ion battery.
In the scheme of the invention, the protective layer covered on the surface of the negative electrode of the water-based zinc ion battery is a compact and uniform protective layer which is built in situ on the interface layer of the negative electrode by inducing the self-assembly of silk fibroin molecules by lysozyme. In addition, silk fibroin and lysozyme are two natural proteins, and the sources are wide, so that the method is environment-friendly. The in-situ constructed negative electrode interface protective layer has various polar functional groups, promotes zinc ions to uniformly deposit and nucleate at the negative electrode interface, and effectively inhibits electrochemical side reactions on the surface of a zinc negative electrode, thereby effectively relieving the problems of growth, corrosion, passivation and capacity attenuation of negative electrode dendrites. Therefore, the protein nano negative electrode protective layer constructed by the silk fibroin and the lysozyme has great application prospect for the large-scale production of the water-based zinc ion battery with high circulation stability.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a preparation method of a water-based zinc ion battery anode with an interface protection layer covered on the surface, which comprises the following steps:
s1: preparing a silk fibroin aqueous solution;
s2: preparing and treating a lysozyme aqueous solution to obtain a treated lysozyme aqueous solution;
s3: mixing the treated lysozyme aqueous solution with the silk fibroin aqueous solution in the step S1 to obtain a silk fibroin and lysozyme mixed solution;
s4: after the zinc cathode is placed on the surface of a mixed solution of silk fibroin and lysozyme or in the solution for incubation for a period of time, a silk fibroin/lysozyme protein nano film is formed on the surface of the zinc cathode in situ, and the silk fibroin/lysozyme protein nano film is an interface protection layer covering the surface of the zinc cathode.
Further, in some embodiments of the invention, in the step S1, the mass fraction of the aqueous silk fibroin solution is 0.1 to 10%.
Further, in some embodiments of the invention, in the step S1, the aqueous silk fibroin solution is obtained by a method comprising: degumming, dissolving, filtering and desalting natural mulberry silk to obtain 0.1-10% silk fibroin aqueous solution.
Further, in some embodiments of the invention, in the step S1, the degumming means during the preparation of the aqueous silk fibroin solution includes, but is not limited to, naCO 3 Degumming and NaHCO 3 Degumming.
Further, in some embodiments of the invention, in the step S1, the silk fibroin aqueous solution is prepared by dissolving silk fibroin in a manner including, but not limited to, liBr.
Further, in some embodiments of the present invention, in the step S2, the processing means: and adding a tris (2-carboxyethyl) phosphine hydrochloride solution diluted by a buffer solution into the lysozyme aqueous solution to obtain a treated lysozyme aqueous solution.
Further, in some embodiments of the present invention, before the mixed solution of silk fibroin and lysozyme is obtained in step S3, the silk fibroin, lysozyme and tris (2-carboxyethyl) phosphine hydrochloride are diluted with neutral buffers, respectively, including but not limited to buffers such as PBS (phosphate buffer), DPBS (durum phosphate buffer) and HBSS (Hanks balanced salt solution).
Further, in some embodiments of the present invention, in the step S3, the mass ratio of the silk fibroin to the lysozyme in the mixed solution of silk fibroin and lysozyme is 0.001:1 to 1:0.001, preferably 0.01:1 to 1:0.01, more preferably 0.1:1 to 1:0.1, still more preferably 0.5:1 to 1:0.5.
Further, in some embodiments of the invention, in the step S3, the mixed solution of silk fibroin and lysozyme is mixed by a method including, but not limited to, shaking, ultrasonic mixing and stirring with a glass rod.
Further, in some embodiments of the present invention, in the step S4, the preparation process of forming the silk protein/lysozyme protein nano film on the surface of the zinc anode in situ is as follows: and (3) carrying out surface treatment on the zinc cathode, then placing the zinc cathode in a mixed solution of silk fibroin and lysozyme, taking out after incubation for a period of time, and drying to form an interface protection layer on the surface of the zinc cathode. The interface protective layer is a silk protein/lysozyme protein nano film formed on the surface of the zinc cathode in situ.
Further, in some embodiments of the present invention, in the step S4, the zinc anode is first surface-treated by, but not limited to, washing with ethanol or acetone and drying.
Further, in some embodiments of the present invention, in the step S4, the zinc anode may be one of a one-dimensional zinc wire, a two-dimensional zinc sheet, and a three-dimensional zinc stent.
Further, in some embodiments of the present invention, in the step S4, the incubation time of the aqueous zinc-ion battery anode protective layer is 1 to 72 hours, preferably 1 to 48 hours, and more preferably 1 to 4 hours.
Further, in some embodiments of the present invention, in the step S4, the drying manner of the aqueous zinc ion battery anode protective layer includes, but is not limited to, drying in an oven at a temperature.
The invention further provides a water-based zinc ion battery anode with the surface covered with the interface protection layer, which is prepared based on the preparation method, wherein the water-based zinc ion battery anode comprises a zinc anode and the interface protection layer with the surface covered with the zinc anode.
The invention further provides a water-based zinc ion battery, which comprises a water-based zinc ion battery anode with the surface covered with the interface protection layer.
Further, in some embodiments of the present invention, the specific preparation method for encapsulating the aqueous zinc ion battery anode with the surface covered with the interface protection layer into a full battery comprises: and placing the water-based zinc ion battery cathode with the surface covered with the interface protection layer into a positive electrode shell, placing a diaphragm, dripping electrolyte until the diaphragm is completely soaked, sequentially placing the water-based zinc ion battery cathode with the surface covered with the interface protection layer, a stainless steel gasket, a stainless steel spring plate and a negative electrode shell, and then placing into a press machine for pressure packaging to obtain the water-based zinc ion symmetrical battery.
The invention provides a water-based zinc ion battery anode with an interface protection layer covered on the surface and a preparation method thereof.
The materials for the negative electrode protective layer of the water-based zinc ion battery are natural biomacromolecule silk fibroin and lysozyme. The negative electrode protective layer provided by the invention is formed by inducing self-assembly of silk fibroin molecules by lysozyme, and is compact and uniform in situ at a negative electrode interface. And a large number of polar groups in protein molecules in the interface layer are utilized to regulate and control uniform deposition of negative zinc ions, so that dendrite growth and passivation of the negative interface layer are effectively relieved. In addition, the uniform and compact interface layer with certain mechanical strength can effectively limit dendrite growth and isolate free water from corroding the cathode, thereby improving the cycle stability of the water-based zinc ion battery, and ensuring that the water-based zinc ion battery is in a range of 10mA cm -2 Can be stably cycled for 1100 hours at a high current density of 5C, and is assembled into a zinc-manganese dioxide battery cycle at a high rate of 5C2000 circles, the capacity is kept at 80 percent, the cycle performance is very stable, and the cycle performance is excellent under different multiplying powers. The water-based zinc ion battery cathode with the surface covered with the interface protection layer has the advantages of simple preparation process, low cost, more environment-friendly material and effective extension of the cycle life and the cycle stability of the zinc ion battery cathode.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) According to the invention, lysozyme is utilized to induce self-assembly of silk fibroin molecules, a compact and uniform interface protection film is generated at the interface of the negative electrode in situ, and a large number of polar groups in the protein molecules are utilized to regulate zinc ions to uniformly deposit and nucleate on the negative electrode, so that the problem of uneven deposition of the negative electrode is effectively solved;
(2) The water-based zinc ion battery cathode with the surface covered with the interface protection layer effectively improves the interface environment of the cathode, improves the wettability of the battery cathode to electrolyte, reduces the corrosion effect of free water in the electrolyte on the cathode, and greatly reduces the occurrence of side reaction of the interface of the cathode;
(3) The protein nano protection layer prepared by the method has excellent stability and high ionic conductivity, and effectively improves the stability of the battery in the long-acting cycle process;
(4) The water-based zinc ion battery cathode with the surface covered with the protein nano-film interface protective layer improves the cycle performance and the multiplying power performance of the water-based zinc ion battery, and the Zn-Zn symmetrical battery stably circulates for more than 6000 hours;
(5) The protein nano protective layer can be also applied to various ion secondary batteries such as magnesium, aluminum and the like;
(6) The water system zinc ion battery cathode containing the protein nano film protective layer with the surface covered can effectively improve the cycle performance of the water system zinc ion battery, so that the water system zinc ion battery has a good and stable charge and discharge process, has excellent performance under high current density, has obvious effect on inhibiting zinc dendrites, and is beneficial to realizing commercialization of the water system zinc ion battery.
Drawings
FIG. 1 is a graph showing the contrast of the wettability of an unmodified zinc sheet and a protein film modified zinc sheet with respect to an electrolyte;
FIG. 2 is a graph of constant current charge and discharge data of a protein film modified zinc anode and an unmodified zinc anode symmetric battery at a current density of 5 mAh;
FIG. 3 is a graph of constant current charge and discharge data for a protein film modified zinc anode and unmodified zinc anode symmetric cell at a current density of 10 mAh;
FIG. 4 is a graph showing the ratio performance of a full cell of a protein film modified zinc anode versus an unmodified zinc anode;
FIG. 5 is a graph of constant current charge and discharge data for a three-dimensional protein film modified zinc anode and an unmodified three-dimensional zinc anode symmetric cell at a current density of 10 mAh;
FIG. 6 is a surface topography under a field emission scanning electron microscope of a zinc anode obtained by incubating a zinc sheet with a protein solution alone;
FIG. 7 is a graph showing the comparison of the surface morphology of zinc flakes and protein film modified zinc flakes under a field emission scanning electron microscope.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
The first embodiment provides a method for preparing a zinc anode with a surface covered with a protein nano film, which comprises the following steps:
s1, preparing a silk fibroin aqueous solution, which specifically comprises the following steps: boiling silk for 1h with 0.5wt% sodium carbonate solution for degumming, washing, drying, dissolving with 9.3M lithium bromide solution, filtering with 300 mesh filter membrane, and desalting with 14000Da dialysis bag to obtain regenerated silk fibroin aqueous solution with concentration of 4%.
S2, diluting the lysozyme aqueous solution and the silk fibroin aqueous solution in the S1, wherein the preparation of the silk fibroin and lysozyme mixed solution specifically comprises the following steps: the aqueous silk fibroin solution was diluted with 4-hydroxyethyl piperazine ethane sulfonic acid buffer to a final concentration of 5mg/mL. Dissolving tris (2-carboxyethyl) phosphine hydrochloride in the buffer solution to make the molar mass of the tris (2-carboxyethyl) phosphine hydrochloride buffer solution be 50mM, and adjusting the pH value to 7.0 by NaOH; dissolving lysozyme in the buffer solution to enable the mass concentration of the lysozyme to be 5mg/mL; and sequentially and uniformly mixing three solutions with equal volumes, and placing the three solutions in a container, wherein the mass ratio of the silk fibroin to the lysozyme is 1:1.
S3, placing the zinc cathode on the surface of the solution or in the solution, and after incubation for a period of time, forming the silk protein/lysozyme protein nano film on the surface of the zinc cathode in situ. The method comprises the following steps: placing a zinc sheet on the surface of the mixed solution for 2 hours, taking out the surface of the zinc sheet, flushing with deionized water, and airing at the ambient temperature and humidity to obtain a zinc anode with the surface covered with the protein nano film;
the reference negative electrode is a zinc sheet which is not subjected to surface modification, and electrolyte wettability test is performed. The method comprises the following steps: the wettability of the zinc sheet coated with the protein nano film and the unmodified zinc sheet to the zinc sulfate electrolyte was tested by using a contact angle experiment. As can be seen from fig. 1, the wettability of the zinc sheet covered by the protein nano film to the electrolyte is obviously better than that of the zinc sheet which is not modified. The protein nano film with a large number of polar groups on the surface can effectively improve the wettability of electrolyte on the negative electrode, optimize the ion beam on the surface of the negative electrode, thereby effectively relieving the non-uniform deposition behavior of the negative electrode ions and improving the cycle performance of the battery.
Example two
The second embodiment provides a method for preparing a negative plate with a surface covering protein nano film, and testing the cycle performance of the negative plate, which comprises the following steps:
s1, preparing a silk fibroin aqueous solution, which specifically comprises the following steps: boiling silk for 45min with 0.5wt% sodium bicarbonate solution, degumming, washing, drying, dissolving with 9.3M lithium bromide solution, filtering with 300 mesh filter membrane, desalting with 14000Da dialysis bag to obtain 4% regenerated silk fibroin aqueous solution, and further diluting 4% regenerated silk fibroin aqueous solution with deionized water to obtain 0.1% silk fibroin aqueous solution.
S2, diluting the lysozyme aqueous solution and the silk fibroin aqueous solution in the S1, wherein the preparation of the silk fibroin and lysozyme mixed solution specifically comprises the following steps: the aqueous silk fibroin solution was diluted with 4-hydroxyethyl piperazine ethane sulfonic acid buffer to a final concentration of 5mg/mL. Dissolving tris (2-carboxyethyl) phosphine hydrochloride in the buffer solution to make the molar mass of the tris (2-carboxyethyl) phosphine hydrochloride buffer solution be 50mM, and adjusting the pH value to 7.0 by NaOH; dissolving lysozyme in the buffer solution to enable the mass concentration of the lysozyme to be 5mg/mL; and sequentially and uniformly mixing three solutions with equal volumes, and placing the three solutions in a container, wherein the mass ratio of the silk fibroin to the lysozyme is 1:1.
S3, placing the zinc cathode on the surface of the solution or in the solution, and after incubation for a period of time, forming the silk protein/lysozyme protein nano film on the surface of the zinc cathode in situ. The method comprises the following steps: placing a zinc sheet on the surface of the mixed solution for incubation for 1h, taking out the surface of the zinc sheet, flushing with deionized water, and airing at the ambient temperature and humidity to obtain a zinc anode with the surface covered with the protein nano film;
further, preparing a 2M zinc sulfate aqueous solution as an electrolyte;
further, the reference negative electrode is a zinc sheet which is not subjected to surface modification;
and assembling the battery. The method comprises the following steps: and placing the negative electrode plate with the surface covered with the protein nano film into a positive electrode shell, then placing a diaphragm, dripping electrolyte until the diaphragm is completely soaked, then sequentially placing the negative electrode plate with the surface covered with the protein nano film, a stainless steel gasket, a stainless steel elastic sheet and the negative electrode shell, and then placing the negative electrode plate with the surface covered with the protein nano film into a press machine for pressure packaging, thus obtaining the water-based zinc ion symmetrical battery.
Specifically, the untreated zinc sheet negative electrode is used for replacing the negative electrode sheet with the surface covered with the protein nano film, and the water system zinc ion symmetric battery is assembled in the same way.
Specifically, electrochemical performance tests are respectively carried out on the aqueous zinc ion battery assembled by the negative plate covered with the protein nano film and the reference negative plate, constant current charge and discharge tests are carried out on the aqueous zinc ion battery, and the set current density is 10mAh cm -2 。
As can be seen from comparison of the results of the symmetrical battery cycle test of FIG. 2, the usage tableThe water-based zinc ion battery of the negative plate with the surface covered with the protein nano film is 10mAh cm -2 The cycle time is obviously improved under the current density, which shows that the cathode of the surface covering protein nano film effectively improves the cycle stability of the battery; the reason is that the negative electrode of the surface covering protein nano film in the embodiment can effectively regulate and control the deposition behavior of ions on the surface of the electrode, reduce the corrosion action of the negative electrode of free water and reduce the growth of dendrites, so that the tested water-based zinc ion battery has more excellent multiplying power performance and cycle stability.
Example III
The third embodiment provides a method for preparing a negative plate of a surface-coated protein nano film, which uses different buffers to prepare the negative plate of the surface-coated protein nano film and tests the cycle performance of the negative plate, and comprises the following steps:
s1, preparing a silk fibroin aqueous solution, which specifically comprises the following steps: boiling silk for 1h with 0.5wt% sodium carbonate solution for degumming, washing, drying, dissolving with 9.3M lithium bromide solution, filtering with 300 mesh filter membrane, and desalting with 14000Da dialysis bag to obtain regenerated silk fibroin aqueous solution with concentration of 4%.
S2, diluting the lysozyme aqueous solution and the silk fibroin aqueous solution in the S1, wherein the preparation of the silk fibroin and lysozyme mixed solution specifically comprises the following steps: the aqueous silk fibroin solution was diluted with PBS and phosphate buffer to a final concentration of 5mg/mL by mass. Dissolving tris (2-carboxyethyl) phosphine hydrochloride in the buffer solution to make the molar mass of the tris (2-carboxyethyl) phosphine hydrochloride buffer solution be 50mM, and adjusting the pH value to 7.0 by NaOH; dissolving lysozyme in the buffer solution to enable the mass concentration of the lysozyme to be 5mg/mL; and sequentially and uniformly mixing three solutions with equal volumes, and placing the three solutions in a container, wherein the mass ratio of the silk fibroin to the lysozyme is 1:1.
S3, placing the zinc cathode on the surface of the solution or in the solution, and after incubation for a period of time, forming the silk protein/lysozyme protein nano film on the surface of the zinc cathode in situ. The method comprises the following steps: placing a zinc sheet on the surface of the mixed solution for 2 hours, taking out the surface of the zinc sheet, flushing with deionized water, and airing at the ambient temperature and humidity to obtain a zinc anode with the surface covered with the protein nano film;
further, preparing a 2M zinc sulfate aqueous solution as an electrolyte;
further, the reference negative electrode is a zinc sheet which is not subjected to surface modification;
specifically, a zinc sheet with a surface covered protein film prepared by phosphate buffer solution and a zinc sheet without surface modification are respectively used as a negative electrode, and the water-based zinc ion symmetrical battery is assembled in the same way.
Specifically, electrochemical performance tests are respectively carried out on the aqueous zinc ion battery assembled by the negative plate covered with the protein nano film and the reference negative plate, constant current charge and discharge tests are carried out on the aqueous zinc ion battery, and the set current density is 5mAh cm -2 。
As can be seen from the symmetric cell cycle data of fig. 3, the negative electrode prepared using the phosphate buffer solution still exhibited stable cycle performance at 5mAh cm -2 The stable circulation is carried out for more than 1400 hours under the condition, compared with the zinc cathode without modification, the circulation time is improved by more than 14 times, and the circulation performance of the cathode is greatly improved.
Example IV
The fourth embodiment provides a method for preparing a three-dimensional negative plate with a surface covering protein nano film, and the method performs a rate performance test, and comprises the following steps:
s1, preparing a silk fibroin aqueous solution, which specifically comprises the following steps: boiling silk for 1h with 0.5wt% sodium carbonate solution for degumming, washing, drying, dissolving with 9.3M lithium bromide solution, filtering with 300 mesh filter membrane, and desalting with 14000Da dialysis bag to obtain regenerated silk fibroin aqueous solution with concentration of 4%.
S2, diluting the lysozyme aqueous solution and the silk fibroin aqueous solution in the S1, wherein the preparation of the silk fibroin and lysozyme mixed solution specifically comprises the following steps: the aqueous silk fibroin solution was diluted with 4-hydroxyethyl piperazine ethane sulfonic acid buffer to a final concentration of 5mg/mL. Dissolving tris (2-carboxyethyl) phosphine hydrochloride in the buffer solution to make the molar mass of the tris (2-carboxyethyl) phosphine hydrochloride buffer solution be 50mM, and adjusting the pH value to 7.0 by NaOH; dissolving lysozyme in the buffer solution to enable the mass concentration of the lysozyme to be 5mg/mL; and sequentially and uniformly mixing three solutions with equal volumes, and placing the three solutions in a container, wherein the mass ratio of the silk fibroin to the lysozyme is 1:0.5.
And S3, electroplating zinc on the three-dimensional foam copper surface by adopting an electrochemical deposition method to obtain the three-dimensional zinc cathode. And placing the three-dimensional zinc cathode in the solution, and after a period of incubation, forming a silk protein/lysozyme protein nano film on the surface of the zinc cathode in situ. The method comprises the following steps: placing the three-dimensional zinc cathode in the mixed solution for incubation for 3 hours, taking out the three-dimensional zinc cathode, flushing the surface with deionized water, and drying in a baking oven at 40 ℃ to obtain the three-dimensional zinc cathode with the surface covered with the protein nano film;
further, preparing 2M zinc sulfate and 0.1M manganese sulfate aqueous solution as electrolyte;
further, the reference negative electrode is a three-dimensional zinc negative electrode which is not modified;
specifically, the battery is assembled by placing a manganese dioxide positive plate into a positive electrode shell, then placing a diaphragm, dripping electrolyte until the diaphragm is completely soaked, then sequentially placing a three-dimensional zinc negative electrode with a protein nano film covered on the surface or a three-dimensional zinc negative electrode which is not treated, a stainless steel gasket, a stainless steel elastic sheet and a negative electrode shell, and then placing the three-dimensional zinc negative electrode, the stainless steel gasket, the stainless steel elastic sheet and the negative electrode shell into a press machine for pressure packaging, thus obtaining the water-based zinc ion/manganese dioxide battery.
Specifically, the three-dimensional zinc negative electrode using the surface-coated protein nano film and the aqueous zinc ion battery of the reference three-dimensional zinc negative electrode were subjected to a rate charge-discharge electric test, respectively, with the set rates of 0.5C, 1C, 2C, 5C and 10C. In addition, the water-based zinc ion battery assembled by the three-dimensional negative electrode is subjected to constant-current charge and discharge test, and the set current density is 10mA cm -2 。
As can be seen from comparison of the rate performance test results of FIG. 4, the discharge capacity and discharge at current densities of 0.5C, 1C, 2C, 5C and 10C of the aqueous zinc ion battery using the three-dimensional zinc anode with the surface-coated protein nano filmThe capacity stability is obviously better than that of the water-based zinc ion battery using the reference three-dimensional zinc cathode. Furthermore, a comparison of the cycle data of FIG. 5 shows that at 10mAh cm -2 Is stable for more than 1100 hours. The three-dimensional zinc cathode with the surface covered by the protein nano film is shown to effectively improve the cycle and rate capability of the battery; the reason is that the negative electrode of the surface covering protein nano film in the embodiment can effectively regulate and control the deposition behavior of ions on the surface of the electrode, reduce the corrosion action of the negative electrode of free water and reduce the growth of dendrites, so that the tested water-based zinc ion battery has more excellent multiplying power performance and cycle stability.
Example five
This example five was used as a comparative example to prepare a negative electrode protective layer using a silk fibroin solution alone, comprising the steps of:
s1, preparing a silk fibroin aqueous solution, which specifically comprises the following steps: boiling silk for 1h with 0.5wt% sodium carbonate solution for degumming, washing, drying, dissolving with 9.3M lithium bromide solution, filtering with 300 mesh filter membrane, and desalting with 14000Da dialysis bag to obtain regenerated silk fibroin aqueous solution with concentration of 4%.
S2, placing the zinc cathode on the surface of a 4% silk fibroin aqueous solution or in the solution, and incubating for a period of time. The method comprises the following steps: placing a zinc sheet on the surface of the 4% silk fibroin aqueous solution for 2 hours, taking out the surface of the zinc sheet, flushing the surface with deionized water, and airing at the ambient temperature and humidity to obtain a zinc anode;
as shown in fig. 6, the surface morphology of the zinc cathode obtained by incubating the aqueous solution of silk fibroin under the field emission scanning electron microscope has a large number of cracks, and the zinc cathode is easily dissolved out when encountering the electrolyte, so that the cathode cannot be effectively protected. And FIG. 7 is a morphology diagram of a self-assembled structure of macromolecules on the surface of the negative electrode protective layer prepared in examples 1-4, wherein the protein protective coating formed by in-situ self-assembly on the surface of the electrode is uniform and compact, and the electrode with different morphologies can be modified. In addition, the protective film formed by in-situ self-assembly has strong acting force with the surface of the electrode, and can stably exist in the long-term use process after the battery is packaged.
According to the invention, lysozyme is selected to induce silk protein self-assembly, and a negative electrode interface protective layer is constructed in situ at a negative electrode interface, so that the problems of uneven zinc ion deposition and zinc dendrite growth of a zinc metal negative electrode are solved. Has better affinity to electrolyte; the zinc ion deposition on the zinc metal surface is facilitated, zinc dendrite is restrained, and the corrosion of free water in the electrolyte to the negative electrode is prevented; the cycle performance of the zinc metal battery is effectively improved; zinc metal batteries have higher coulombic efficiency at the same rate.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. The preparation method of the water-based zinc ion battery anode with the surface covered with the interface protection layer is characterized by comprising the following steps of:
s1: preparing a silk fibroin aqueous solution;
s2: preparing and treating a lysozyme aqueous solution to obtain a treated lysozyme aqueous solution;
s3: mixing the treated lysozyme aqueous solution with the silk fibroin aqueous solution in the step S1 to obtain a silk fibroin and lysozyme mixed solution;
s4: after the zinc cathode is placed on the surface of a mixed solution of silk fibroin and lysozyme or in the solution for incubation for a period of time, a silk fibroin/lysozyme protein nano film is formed on the surface of the zinc cathode in situ, and the silk fibroin/lysozyme protein nano film is an interface protection layer covering the surface of the zinc cathode.
2. The method for producing a negative electrode for an aqueous zinc-ion battery having a surface covered with an interface protective layer according to claim 1, wherein in the step S1, the mass fraction of the aqueous silk fibroin solution is 0.1 to 10%.
3. The method for preparing a negative electrode of an aqueous zinc-ion battery covered with an interface protection layer according to claim 1, wherein in the step S2, the treatment means: and adding a tris (2-carboxyethyl) phosphine hydrochloride solution diluted by a buffer solution into the lysozyme aqueous solution to obtain a treated lysozyme aqueous solution.
4. The method for preparing the negative electrode of the water-based zinc ion battery with the surface covered with the interface protection layer according to claim 1, wherein before the mixed solution of the silk fibroin and the lysozyme is obtained in the step S3, the silk fibroin, the lysozyme and the tris (2-carboxyethyl) phosphine hydrochloride are respectively diluted by a neutral buffer solution, wherein the neutral buffer solution is selected from PBS, DPBS or HBSS buffer solution.
5. The method according to claim 1, wherein in the step S3, the mass ratio of the silk fibroin to the lysozyme in the mixed solution of silk fibroin and lysozyme is 0.001:1-1:0.001, preferably 0.01:1-1:0.01, more preferably 0.1:1-1:0.1, still more preferably 0.5:1-1:0.5.
6. The method for preparing the water-based zinc ion battery anode with the surface covered with the interface protection layer according to claim 1, wherein in the step S4, the preparation process of forming the silk protein/lysozyme protein nano film on the surface of the zinc anode in situ is as follows: and (3) carrying out surface treatment on the zinc cathode, then placing the zinc cathode in a mixed solution of silk fibroin and lysozyme, taking out after incubation for a period of time, and drying to form an interface protection layer on the surface of the zinc cathode.
7. The method for preparing a negative electrode of a water-based zinc ion battery with an interface protection layer covered on the surface, according to claim 1, wherein in the step S4, the negative electrode is one of a one-dimensional zinc wire, a two-dimensional zinc sheet and a three-dimensional zinc bracket.
8. The method for producing a negative electrode of an aqueous zinc-ion battery covered with an interface protective layer according to claim 1, wherein in the step S4, the incubation time of the negative electrode protective layer of the aqueous zinc-ion battery is 1 to 72 hours, preferably 1 to 48 hours, and more preferably 1 to 4 hours.
9. The aqueous zinc ion battery anode with the surface covered with the interface protection layer prepared by the preparation method according to any one of claims 1 to 8 is characterized in that the aqueous zinc ion battery anode comprises a zinc anode and the interface protection layer with the surface covered with the zinc anode.
10. An aqueous zinc ion battery comprising the surface-coated interface protective layer of claim 9.
CN202310192404.4A 2023-03-02 2023-03-02 Water-based zinc ion battery cathode with surface covered with interface protection layer and preparation method thereof Pending CN116344730A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116666638A (en) * 2023-07-24 2023-08-29 首都师范大学 Artificial solid/liquid interface protective layer based on layer-by-layer self-assembly technology, metal electrode, battery, and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116666638A (en) * 2023-07-24 2023-08-29 首都师范大学 Artificial solid/liquid interface protective layer based on layer-by-layer self-assembly technology, metal electrode, battery, and preparation method and application thereof
CN116666638B (en) * 2023-07-24 2024-01-23 首都师范大学 Water system zinc ion secondary battery

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