CN114843628A - Zinc ion battery and preparation method thereof - Google Patents

Zinc ion battery and preparation method thereof Download PDF

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Publication number
CN114843628A
CN114843628A CN202210575014.0A CN202210575014A CN114843628A CN 114843628 A CN114843628 A CN 114843628A CN 202210575014 A CN202210575014 A CN 202210575014A CN 114843628 A CN114843628 A CN 114843628A
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zinc
ion battery
anode
temperature
composite material
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陈张伟
涂勇强
伊德思
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Shenzhen University
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Shenzhen 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a zinc ion battery and a preparation method thereof, wherein the zinc ion battery comprises a shell injected with electrolyte, an anode, a diaphragm and a cathode which are sequentially arranged in the shell at intervals, wherein the shell is provided with an upper cover with a pouring gate; the anode consists of zinc and stainless steel foil and a composite material coating deposited on one side of the zinc and stainless steel foil, wherein the composite material coating comprises a PC/SiOC composite material, and the PC/SiOC composite material consists of porous carbon and a silicon-oxygen-carbon network interpenetrating the porous carbon. The composite material coating improves the transmission speed of zinc ions on the surface of the anode, and has the characteristics of high conductivity and high electrochemical activity, so that the capacity and rate performance of the zinc ion battery are improved, the transmission speed of the zinc ions is high, the diffusion area is large, the growth of dendrites can be effectively inhibited, and the cycle life of the battery is greatly prolonged.

Description

Zinc ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of zinc ion batteries, in particular to a zinc ion battery and a preparation method thereof.
Background
Under the background that the traditional energy resources are in shortage and cause environmental pollution, the demand of consumer-grade electronic products is increasing day by day, electric vehicles are developing steadily and renewable energy sources are connected in a grid, people continuously increase the demand of environment-friendly energy storage equipment with high energy density, recyclability, low cost and high reliability. Among various energy storage devices, lithium ion batteries have been dominant in the commercial secondary battery market due to their high energy density and long cycle life. However, the lithium ion battery has inherent problems of flammability of organic electrolyte, short circuit explosion risk caused by dendrite growth of electrodes, strict requirements on manufacturing and assembly, scarce lithium resources and the like, and the large-scale application of the lithium ion battery is seriously influenced. As a new alternative energy storage technology with great development prospect, the rechargeable water zinc ion battery has the advantages of high theoretical capacity (820mAh/g), low oxidation-reduction potential (-0.76Vvs. SHE), abundant reserves, simple manufacture and assembly, low cost, safety, environmental protection and the like, shows great potential in portable electronic application and large-scale energy storage systems, and has wide application prospect.
However, zinc ion batteries face a great challenge in practical application, and in particular, dendritic growth of a metal zinc anode during cyclic deposition/stripping is the biggest problem limiting the application of the zinc ion batteries: the dendritic crystal continuously consumes water during the circulation process to generate an irreversible byproduct, so that the zinc ion battery has low coulombic efficiency, low capacity and limited cycle life; meanwhile, along with the growth of the dendrite, the surface area of the anode is increased, so that the corrosion of the anode and other surface-related reactions are increased, the anode is continuously consumed, and the performance reduction speed of the battery is accelerated; more seriously, too long dendrites can penetrate the separator causing short circuit failure of the cell. In order to solve the problem of dendrite growth of the anode to improve the cycle life and rate performance of the zinc ion battery, various methods for preparing the anode of the zinc ion battery considering the inhibition of dendrite growth have been developed, such as: liu et al developed a method for inhibiting dendritic crystal growth by coating graphene oxide nanosheets on a zinc metal anode using a casting method; the invention application CN114094035A discloses a preparation method of an aluminum-zinc alloy coating of an anode of a zinc ion battery, which utilizes a magnetron co-sputtering technology to prepare the aluminum-zinc alloy coating on the anode for protecting the anode; the invention application CN112952052A provides a zinc/carbon nanotube foam composite material as the anode material of zinc ion battery and discloses a method for preparing anode by high temperature reaction and electrodeposition method using the composite material in the invention application CN 112952053A.
However, the above-mentioned existing zinc ion battery technologies have the following disadvantages: the transmission speed of zinc ions on the surface of the anode is slow, and the conductivity and the electrochemical activity are not high, so that the capacity and the rate performance of the battery are limited; the limited diffusion area of zinc ions cannot completely inhibit the growth of dendrites, and the risk of short circuit caused by generation of dendrites still exists, so that the cycle life is limited; the preparation process is complex and has high cost.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a zinc ion battery and a preparation method thereof, and aims to solve the problems that dendrites are easy to grow on the surface of an anode of the conventional zinc ion battery, the capacity and rate capability of the battery are poor, and the cycle life is short.
The technical scheme of the invention is as follows:
a zinc ion battery comprises a shell injected with electrolyte, and an anode, a diaphragm and a cathode which are sequentially arranged in the shell at intervals, wherein an upper cover with a pouring gate is arranged on the shell, a negative terminal is welded at the upper end of the anode, a positive terminal is welded at the upper end of the cathode, and a sealing cover is arranged at the pouring gate of the upper cover; the positive pole is in by zinc and stainless steel foil and deposit zinc and stainless steel foil composite coating one side constitute, the grid body coating of middle fretwork that the composite coating is for arranging by a plurality of horizontal poles and a plurality of montants are even crisscross to be constituteed, the composite coating adopts the low temperature to write directly 3D printing technique printing ink and forms, the ink includes N-methyl pyrrolidone and dissolves PC/SiOC combined material, polyvinylidene fluoride and conductive carbon black in the N-methyl pyrrolidone, PC/SiOC combined material is in by porous carbon and interpenetrating silica carbon network on the porous carbon constitutes.
The zinc ion battery is characterized in that the electrolyte is ZnSO 4 Deionized water solution.
The zinc ion battery is characterized in that the diaphragm is a polypropylene separator, and the cathode is V 2 O 5 a/C plate.
The zinc ion battery is characterized in that the positive terminal and the negative terminal are made of copper-based silver-plated alloy.
The middle hollow part of the zinc ion battery is a square hollow part, the side length of the square hollow part is equal to the line width of the transverse rod and the vertical rod, the transverse rod and the vertical rod are the same in size, and the line width is 400-420 mu m.
The zinc ion battery is characterized in that the thickness of the zinc and the stainless steel foil is 0.1mm, and the thickness of the composite material coating is 500-550 mu m.
A preparation method of a zinc ion battery comprises the following steps:
performing ball milling treatment on a PC/SiOC composite material, polyvinylidene fluoride and conductive carbon black, and dissolving the PC/SiOC composite material, polyvinylidene fluoride and conductive carbon black in N-methyl pyrrolidone to obtain an ink composition, wherein the PC/SiOC composite material consists of porous carbon and a silicon-oxygen-carbon network interpenetrating the porous carbon;
removing lumps and large particles in the ink composition by vacuum filtration, and standing at room temperature for a predetermined time to obtain ink;
printing the ink on one surface of zinc and stainless steel foil by using a low-temperature direct-writing 3D printing technology, and drying in vacuum to obtain an anode;
sequentially installing the anode, the diaphragm and the cathode in a shell, and installing an upper cover with a pouring port on the shell;
welding a positive terminal at the upper end of the cathode, welding a negative terminal at the upper end of the anode, and injecting electrolyte from a pouring port of the upper cover until the electrolyte is filled;
and installing a sealing cover at the pouring gate of the upper cover to obtain the zinc ion battery.
The preparation method of the zinc ion battery comprises the following steps of printing the ink on one surface of zinc and stainless steel foil by using a low-temperature direct-writing 3D printing technology, and drying in vacuum to obtain the dendrite-free anode of the zinc ion battery, wherein the dendrite-free anode of the zinc ion battery comprises the following steps:
filling the ink into an injector needle tube connected with a lockable stainless steel blunt nozzle, extruding the ink from the injector needle tube through the lockable stainless steel blunt nozzle, and printing the ink on one surface of zinc and stainless steel foil to obtain an anode of the composite material coating in an uncured state;
and (3) placing the anode of the composite material coating in an uncured state into a vacuum oven, setting the temperature of the vacuum oven to 80 ℃, and keeping the temperature for 12 hours to obtain the dendrite-free anode of the zinc ion battery.
The preparation method of the zinc ion battery comprises the following steps of:
preparation of isoreticular covalently functionalized zirconium-based MOF crystals, namely UiO-66-NH 2 A crystal;
dissolving cetyl trimethyl ammonium bromide in a PDSDA methanol solution in an ultrasonic bath to obtain a PDSDA/CTAB mixed solution; the UiO-66-NH is stirred under magnetic force 2 Dissolving the crystal in methanol to obtain UiO-66-NH 2 A solution;
adding PDSDA/CTAB mixed solution into the UiO-66-NH in an argon atmosphere 2 Stirring the solution at room temperature, then performing argon degassing, sample collection, ethanol washing and vacuum drying after completing the polymerization reaction in MOFs to prepare a UiO-66/PDSDA composition;
the UO-66/PDSDA composition was placed in a tube furnace and subjected to a three-stage pyrolysis process under argon atmosphere: in the first stage, the temperature is raised from 25 ℃ to 400 ℃ at a rate of 2 ℃/min, and then the temperature is maintained at 400 ℃ for two hours; in the second stage, the temperature is increased from 200 ℃ to 800 ℃ at the temperature increase rate of 2 ℃/min, and the temperature is kept at 800 ℃ for four hours; in the third stage, the temperature is reduced from 800 ℃ to room temperature at the temperature reduction rate of 2 ℃/min.
The preparation method of the zinc ion battery comprises the following steps of 2 The preparation of the crystal comprises the steps of:
reacting ZrCl 4 And H 2 N-H 2 BDC is dissolved in HCON (CH) at the same concentration of 0.02mol/L to 0.025mol/L 3 ) 2 Then adding hydrochloric acid, hydrochloric acid and HCON (CH) 3 ) 2 The volume ratio of (1: 140) to obtain a mixed solution;
the mixed solution was stirred at room temperature for 30 minutes and then transferred to a polytetrafluoroethylene-lined autoclave for 10 hours at hydrothermal 120 ℃ after which the yellow powder product was obtained by centrifuging the suspension, followed by washing with absolute ethanol, then transferred to a schlenk flask and dried at ambient temperature to obtain UiO-66-NH 2 And (4) crystals.
Has the advantages that: compared with the prior art, the zinc ion battery prepared by the invention has the characteristics of high transmission speed of zinc ions on the surface of the anode, high conductivity and high electrochemical activity, so that the capacity and rate performance of the battery are improved, and the zinc ion battery can effectively inhibit dendritic crystal growth and greatly prolong the cycle life of the battery by benefiting from the characteristics of large diffusion area of the zinc ions on the surface of the anode and high transmission speed of the zinc ions. The preparation process of the zinc ion battery has the advantages of simplicity, low cost and the like, the anode prepared by the method is used for constructing the complete zinc ion battery, the high capacity of 67mAh/g is still achieved after 2453 times of circulation under the current density of 0.5A/g, the cycle life and the rate capability are good, and the method has great significance for the application of an environment-friendly and safe zinc ion battery energy storage technology and higher practicability.
Drawings
Fig. 1 is a schematic structural diagram of a zinc ion battery of the present invention.
Fig. 2 is a schematic structural diagram of an anode in a zinc-ion battery of the present invention.
Fig. 3 is a flow chart of a method for manufacturing a zinc ion battery according to the present invention.
FIG. 4 is a schematic diagram of the chemical reaction of the PC/SiOC composite material of the present invention.
FIG. 5a is an SEM image of the PC/SiOC composite material obtained in example 1 of the present invention; b is UiO-66-NH obtained in inventive example 1 2 SEM images of the crystals; c is PC alone in example 1 of the present inventionSEM image.
FIG. 6 a is a TEM image of the PC/SiOC composite material obtained in example 1 of the present invention; b is a high resolution TEM image of the PC/SiOC composite material obtained in inventive example 1.
Fig. 7 is a schematic view showing cycle life and rate characteristics of the zinc-ion batteries of example 1, comparative example 1 and comparative example 2 in the present invention at a current density of 0.5A/g.
Detailed Description
The invention provides a zinc ion battery and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1-2, the present invention provides a zinc ion battery, as shown in the figure, including a casing 1 filled with an electrolyte 2, an anode 3, a diaphragm 4 and a cathode 5 sequentially arranged in the casing 1 at intervals, wherein the casing 1 is provided with an upper cover 6 having a pouring gate, the upper end of the anode 3 is welded with a negative terminal 7, the upper end of the cathode 5 is welded with a positive terminal 8, and the pouring gate of the upper cover 6 is provided with a sealing cover 9; the positive pole 3 is in by zinc and stainless steel foil 301 and deposit the combined material coating 302 of zinc and stainless steel foil 301 one side is constituteed, the combined material coating 302 is the grid body coating of the middle fretwork of evenly crisscross the arranging constitution of a plurality of horizontal poles and a plurality of montant, the combined material coating 302 adopts the low temperature to write directly 3D printing technique printing ink and forms, the ink includes N-methyl pyrrolidone and dissolves PC/SiOC combined material, polyvinylidene fluoride and conductive carbon black in the N-methyl pyrrolidone, PC/SiOC combined material is in by porous carbon and interpenetrating silica carbon network on the porous carbon is constituteed.
Specifically, the PC/SiOC composite material has an electrode optimized three-dimensional grid structure, can rapidly invert, bear and guide divalent zinc ions, and simultaneously limits the direct contact of an organic electrolyte and an anode, and has strong molecular coordination, so that a larger rapid diffusion area can be provided for the zinc ions to effectively control the growth of dendrites. Based on the method, the PC/SiOC composite material is prepared into ink, and the ink is printed on the surfaces of zinc and stainless steel foils to form a film by adopting a low-temperature direct-writing 3D printing technology, so that an anode is prepared; and finally assembling the anode, the diaphragm and the cathode into the zinc ion battery. In the invention, the composite material coating 302 can improve the transmission speed of zinc ions on the surface of the anode, and the composite material coating also has the characteristics of high conductivity and high electrochemical activity, so that the capacity and the rate capability of the zinc ion battery are improved, and the characteristics of high transmission speed and large diffusion area of the zinc ions of the composite material coating 302 can effectively inhibit the growth of dendrites and greatly improve the functional requirement of cycle life; the anode prepared by the method is used for constructing a complete zinc ion battery, has high capacity of 67mAh/g after 2453 times of circulation under the current density of 0.5A/g, has good cycle life and rate capability, has great significance for developing a zinc ion battery without dendrites, and has higher practicability.
In this embodiment, the composite material coating 302 is printed to be the grid coating of the middle hollow 21, so that the surface area of the composite material coating is macroscopically increased, that is, the diffusion area of zinc ions is increased, and the growth of dendrites can be further effectively inhibited. That is to say, the dendrite-free anode of the zinc ion battery improves the diffusion area of zinc ions from the macroscopic aspect and the microscopic aspect, and simultaneously improves the transmission speed of the zinc ions, so that the growth of dendrites can be inhibited to the greatest extent, and the functional requirement of the battery on long cycle life is improved.
In some embodiments, the electrolyte is ZnSO 4 Deionized water solution, but not limited thereto; the diaphragm is a polypropylene separator, preferably a 2400 porous polypropylene separator with the thickness of 25 μm from Celgard corporation in America; the cathode is V 2 O 5 A plate of/C, said V 2 O 5 the/C flat plate is formed by depositing V on a carbon flat plate 2 O 5 Coated flat sheet.
In some embodiments, the positive electrode terminal and the negative electrode terminal are made of copper-based silver-plated alloy, which has the advantages of low contact resistance and rust resistance.
In some embodiments, the material of the shell, the upper cover and the sealing cover is ABS engineering plastics, and the material has the advantages of firmness and aging resistance.
In some embodiments, a joint of the upper cover and the shell and a joint of the pouring gate sealing cover and the upper cover are provided with a silicon-fluorine rubber sealing ring to prevent the electrolyte from leaking.
In some embodiments, as shown in fig. 2, the middle hollow is a square hollow having a side length equal to the line width of the cross bar and the vertical bar. In order to ensure that the grid coating formed by printing has the largest surface area and prevent the adjacent cross rods or the adjacent vertical rods from being adhered to each other in the printing process, the embodiment ensures that the side length of the square hollow is equal to the line width of the cross rods and the vertical rods in the printing process. In this embodiment, the dimensions of the cross bar and the vertical bar are the same, and the line widths are all 400-. By way of example, the line widths of the horizontal rods and the vertical rods are 409 μm, and the side lengths of the square hollows are 409 μm.
In some embodiments, the zinc and stainless steel foils are 0.1mm thick and the composite coating is 500-. By way of example, the composite coating may have a thickness of 500 μm, 510 μm, 520 μm, 528 μm, 530 μm, 540 μm, 550 μm, and the like.
In some embodiments, the mass ratio of the PC/SiOC composite, polyvinylidene fluoride, and conductive carbon black is 8:1: 1.
In some embodiments, there is also provided a method of manufacturing a zinc-ion battery, as shown in fig. 3, comprising the steps of:
s10, performing ball milling treatment on a PC/SiOC composite material, polyvinylidene fluoride and conductive carbon black, and dissolving the PC/SiOC composite material, the polyvinylidene fluoride and the conductive carbon black in N-methyl pyrrolidone to obtain an ink composition, wherein the PC/SiOC composite material consists of porous carbon and a silicon-oxygen-carbon network interpenetrating the porous carbon;
s20, removing caking and large particles in the ink composition through vacuum filtration, and standing for a preset time at room temperature to obtain ink;
s30, printing the ink on one surface of zinc and stainless steel foil by using a low-temperature direct-writing 3D printing technology, and drying in vacuum to obtain an anode;
s40, sequentially installing the anode, the diaphragm and the cathode in a shell, and installing an upper cover with a pouring gate on the shell;
s50, welding a positive terminal at the upper end of the cathode, welding a negative terminal at the upper end of the anode, and injecting electrolyte from the pouring gate of the upper cover until the electrolyte is fully filled;
and S60, mounting a sealing cover at the pouring gate of the upper cover to obtain the zinc ion battery.
The preparation process of the zinc ion battery provided by the embodiment has the advantages of being simple to operate, low in cost and the like, the zinc ion battery prepared by the embodiment has the characteristics of high transmission speed of zinc ions on the surface of an anode and high conductivity and electrochemical activity, so that the capacity and rate performance of the zinc ion battery are improved, dendritic crystal growth can be effectively inhibited by the characteristics of high transmission speed of the zinc ions of the composite material coating and large diffusion area, and the cycle life of the battery is greatly prolonged. The anode prepared by the embodiment realizes excellent capacity of more than 500 cycles of 99mAh/g in a half-cell at a current density of 0.45A/g, and the coulombic efficiency is as high as 99.98%; the anode prepared by the method is used for constructing a complete zinc ion battery, has high capacity of 67mAh/g after 2453 times of circulation under the current density of 0.5A/g, has good cycle life and rate capability, has great significance for developing a zinc ion battery without dendrites, and has higher practicability.
In the embodiment, the ink has good viscosity characteristic, shear thinning characteristic and shape retention characteristic, and the anode surface coating obtained by the ink has high dimensional accuracy, smooth surface and good printing performance.
In some embodiments, the step of printing the ink on one side of zinc and stainless steel foil by using a low-temperature direct-writing 3D printing technology, and after vacuum drying treatment, preparing the dendrite-free anode of the zinc-ion battery comprises: slightly stirring the ink, then filling the ink into a 10mL syringe needle tube connected with a lockable stainless steel blunt nozzle with the inner diameter of 200 mu m, then controlling the ink flow rate and the printing speed in a low-temperature direct-writing 3D printer to be 18mm/s by using computer aided design software SolidWorks Corporation, extruding and printing the ink in the syringe needle tube on one surface of zinc and stainless steel foil through the lockable stainless steel blunt nozzle to obtain an anode with an uncured composite material coating; and (3) placing the anode of the composite material coating in an uncured state into a vacuum oven, setting the temperature of the vacuum oven to 80 ℃, and keeping the temperature for 12 hours to obtain a cured anode finished product.
In some embodiments, the preparation of the PC/SiOC composite material comprises the steps of: ZrCl 4 And H 2 N-H 2 BDC is dissolved in HCON (CH) at the same concentration of 0.02mol/L to 0.025mol/L 3 ) 2 Then adding hydrochloric acid, hydrochloric acid and HCON (CH) 3 ) 2 The volume ratio of (1: 140) to obtain a mixed solution; after stirring the mixed solution at room temperature for 30 minutes, the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and heated at 120 ℃ for 10 hours in a hydrothermal manner, after which a yellow powder product was obtained by centrifuging the suspension, which was subsequently washed with absolute ethanol, then transferred to a schlenk flask and dried at ambient temperature to obtain UiO-66-NH 2 A crystal; cetyl trimethylammonium bromide (CTAB) was dissolved in PDSDA (poly (silylene) diacetylene) in an ultrasonic bath]) Obtaining a PDSDA/CTAB mixed solution in a methanol solution; the UiO-66-NH is stirred under magnetic force 2 Dissolving the crystal in methanol to obtain UiO-66-NH 2 A solution; adding PDSDA/CTAB mixed solution into the UiO-66-NH in an argon atmosphere 2 Stirring the solution at room temperature, then performing argon degassing, sample collection, ethanol washing and vacuum drying after completing the polymerization reaction in MOFs to prepare a UiO-66/PDSDA composition; the UO-66/PDSDA composition was placed in a tube furnace and subjected to a three-stage pyrolysis process under argon atmosphere: in the first stage, the temperature is raised from 25 ℃ to 400 ℃ at a rate of 2 ℃/min, and then the temperature is maintained at 400 ℃ for two hours; in the second stage, the temperature is increased from 200 ℃ to 800 ℃ at the temperature increase rate of 2 ℃/min, and the temperature is kept at 800 ℃ for four hours; in the third stage, the first step is that,the temperature is reduced from 800 ℃ to room temperature at the cooling rate of 2 ℃/min, and the PC/SiOC composite material is prepared.
Specifically, as shown in FIG. 4, UiO-66-NH was prepared in this example 2 Crystallizing, and mixing the PDSDA/CTAB mixed solution with the UiO-66-NH 2 The solution is stirred and mixed, during which the linear PDSDA can be mixed with UiO-66-NH 2 On the crystal-NH 2 Reacting to bind the PDSDA to the UiO-66-NH 2 On the crystal, a UiO-66/PDSDA composition is generated; finally, the UO-66/PDSDA composition is subjected to pyrolysis treatment, and in the first stage, polymerization can occur among a plurality of PDSDAs in the UO-66/PDSDA composition and/or polymerization can occur among PDSDAs between adjacent UO-66/PDSDA compositions, so that the PDSDAs on the UO-66 form a cross-linked network; in the second stage, the Si-C bond in the cross-linked network-shaped PDSDA is broken by high-temperature heating, so that an SiOC network is formed, the SiOC network is interpenetrated on a porous carbon matrix, so that the PC/SiOC composite material is formed, the matrix of the PC/SiOC composite material is an MOF framework, and the composite network SiOC structure enlarges the specific surface area, the conductivity, the electrochemical activity and the like of the material, so that the material has great advantages in zinc ion battery anode application.
In this example, CTAB acts as a surfactant to break the intrinsic polymeric attraction between the PDSDA polymer chains, allowing the PDSDA polymer chains to better complex onto the MOF framework to form a UiO-66/PDSDA composition.
In the embodiment, in the mixed solution of PDSDA and CTAB, the concentration of PDSDA is 0.01g/mL, and the concentration of CTAB is 0.005 g/mL; the UiO-66-NH 2 The concentration of the solution is 0.01455 g/mL; PDSDA/CTAB mixed solution and UiO-66-NH 2 The mass ratio of the solution is 1: 3.
The invention is further illustrated by the following specific examples:
example 1
The preparation method of the zinc ion battery comprises the following steps:
s1, preparing the composite material for the anode, which comprises the following specific operations:
s101, adding 1.50g of 6.4mmol of ZrCl 4 And 1.56g,6.4mmol of H 2 N-H 2 BDC dissolved in 280mL HCON (CH) 3 ) 2 Then 2mL of 36 wt% hydrochloric acid was added to make hydrochloric acid and HCON (CH) 3 ) 2 In a volume ratio of 1:140, ZrCl 4 And H 2 N-H 2 The concentration of BDC is 0.023mol/L and is in the range of 0.02mol/L to 0.025 mol/L; the mixed solution was then stirred at room temperature for thirty minutes, after which the mixture was transferred to a 500mL Teflon lined autoclave heated at 120 ℃ for ten hours in a hydrothermal manner to obtain a yellow powder product by centrifuging the suspension after heating, followed by washing with anhydrous ethanol, then transferred to a Schlenk bottle and dried at ambient temperature to obtain UiO-66-NH 2 A crystal;
s102, dissolving 0.5g of CTAB in an ultrasonic bath into 100mL of PDSDA-methanol solution with the concentration of 0.01g/mL and the volume of 100mL for polymerization reaction to obtain a PDSDA/CTAB mixed solution, wherein the concentration of CTAB in the mixed solution is 0.005 g/mL; 1.455g of UiO-66-NH obtained in step S101 was stirred under magnetic force 2 The crystals were dissolved in 100mL of methanol in a Schlenk flask to obtain a concentration of 0.01455g/L of UiO-66-NH 2 A solution;
s103, quickly immersing the PDSDA/CTAB mixed solution obtained in the step S102 in an argon environment according to the mass ratio of 1:3 into a solution containing UiO-66-NH obtained from the step S102 2 In a schlenk flask of the solution, first vigorously stirred at room temperature for thirty minutes, then the polymerization reaction within the MOFs was completed for three hours, then the schlenk flask was degassed with argon, then the sample was collected using a rotary evaporator, washed with ethanol, and finally dried overnight in a vacuum oven set at 80 ℃ to obtain the UiO-66/PDSDA composition;
s104, putting the UiO-66/PDSDA composition obtained in the step S103 into a tube furnace, and carrying out three-stage pyrolysis process in an argon environment: in the first stage, the temperature is raised from 25 ℃ to 400 ℃ at a rate of 2 ℃/min, and then the temperature is maintained at 400 ℃ for two hours; in the second stage, the temperature is increased from 200 ℃ to 800 ℃ at the temperature increase rate of 2 ℃/min, and the temperature is kept at 800 ℃ for four hours; in the third stage, the temperature is reduced from 800 ℃ to room temperature at the temperature reduction rate of 2 ℃/min.
S2, preparing the anode composite material coating ink suitable for 3D printing, and specifically operating as follows:
s201, firstly mixing the PC/SiOC composite material obtained in the step S1 with PVDF and conductive carbon black in a ratio of 8:1:1, and then dissolving the mixed powder in an NMP solution to obtain a homogeneous ink composition;
s202, removing the agglomeration and large particles of the ink composition in the step S201 through vacuum filtration to prevent nozzle blockage, and then standing for twelve hours at room temperature to obtain stable anode composite material coating ink suitable for 3D printing.
S3, printing ink on one side of the zinc foil and the stainless steel foil by using low-temperature direct-writing 3D printing, and specifically operating as follows:
gently stirring the ink obtained in the step S2, then loading the ink into a 10mL syringe needle tube connected with a lockable stainless steel blunt nozzle with the inner diameter of 200 mu m, controlling the ink flow rate and the printing speed in a low-temperature direct-writing 3D printer to be 18mm/S by utilizing computer aided design software SolidWorks Corporation, and extruding and printing the ink in the syringe needle tube on one surface of zinc and stainless steel foil through the lockable stainless steel blunt nozzle to obtain an anode with an uncured composite material coating;
s4, drying the 3D printed anode in a vacuum oven to obtain a cured anode finished product, and specifically: and (5) placing the anode of the composite material coating obtained in the step (S3) in an uncured state into a vacuum oven, setting the temperature of the vacuum oven to 80 ℃, and preserving the heat for 12 hours to obtain a cured anode finished product.
S5, assembling the battery to obtain the complete zinc ion battery, and specifically operating as follows:
s501, using the anode obtained in the step S4 as an anode, a 2400 porous polypropylene separator with a thickness of 25 μ M manufactured by Celgard corporation of America as a separator, and 3M ZnSO 4 Deionized water as electrolyte and V 2 O 5 V of flat coating 2 O 5 the/C flat plate is a cathode, and an anode, a diaphragm and the cathode are arranged in the shell;
s502, mounting an upper cover on the shell;
s503, welding a positive terminal at the upper end of the cathode and welding a negative terminal at the upper end of the anode;
s504, injecting electrolyte from a pouring gate until the electrolyte is fully filled;
and S505, mounting a sprue sealing cover at the sprue of the upper cover to obtain the zinc ion battery.
To verify the cycle life and rate performance of the zinc ion cells fabricated by the method proposed by the present invention, comparative examples were set for electrical performance test comparisons with the complete cell of example 2, and the comparative examples were set as follows:
comparative example 1
In comparative example 1, the battery manufacturing process compared to the process of example 1, the ink was coated flat on one side of the zinc and stainless steel foils in step S3 instead of printing the ink on one side of the zinc and stainless steel foils using the low temperature direct write 3D printing technique, and the zinc ion battery was obtained in the same manner as in example 1.
Comparative example 2
In comparative example 2, the battery manufacturing process was compared to the process of example 1 without performing steps S1 to S4, and zinc and stainless steel foils 0.1mm after without any coating were directly used as anodes, and other steps were the same as in example 1 to obtain a zinc ion battery.
First, the structural properties of the PC/SiOC composite material prepared in the present invention were verified, and the PC/SiOC composite material prepared in example 1 was subjected to characterization of material morphology and structure using a Scanning Electron Microscope (SEM) model JEOL-6700 and a Transmission Electron Microscope (TEM) model JEOL-2100F, while dispersion spectrum analysis (EDS) was performed using an energy dispersive X-ray spectrometer during SEM analysis to obtain detailed information of the element distribution and phase structure of the composite material. The results are as follows: FIG. 5 (a) is an SEM image of a PC/SiOC composite material, showing that ZrO is contained in the composite material 2 The spherical particle diameter of the carbon shell of (a) is about 100nm, and (b) in FIG. 5 is UiO-66-NH obtained in step S1 of example 1 2 SEM image of the crystal, FIG. 5 (c) is SEM image of PC alone, comparing FIG. 5 (a), FIG. 5 (b) and FIG. 5 (c) to see:the morphology of the PC/SiOC composite material remains the same as the original UiO-66-NH after polymerization and pyrolysis 2 The crystal forms are consistent; FIG. 6 (a) is a TEM image of a PC/SiOC composite material, showing that the PC/SiOC composite material retains the parent UiO-66-NH 2 The crystal structure has reserved porosity and is in coordinated arrangement with an SiOC network interpenetrating with the PC surface, and a large number of active sites are created for ion storage; FIG. 6 (b) is a high resolution TEM image of a PC/SiOC composite material, showing that the PC/SiOC composite material has significant threading dislocations, particle clusters and grain boundaries derived from ZrO of different adjacent shells 2 SiOC coordination among crystals, and an interpenetrating SiOC network in PC can be used as a conductive network, so that more active sites are created and the charge transmission performance is improved; the structural performance test of the PC/SiOC composite material can obtain that: the PC/SiOC composite material obtained in the embodiment 1 has an electrode-optimized three-dimensional grid structure, can rapidly invert, bear and guide divalent zinc ions, simultaneously limits direct contact between an organic electrolyte and an anode, has strong molecular coordination, and can provide a larger rapid diffusion region for the zinc ions to effectively control dendritic crystal growth.
Next, the whole cells of example 2 and each comparative example were subjected to electrical property tests and comparisons, and rate capacity and cycle performance tests were performed using a cell tester of LANHE-CT2001A, model number, of wuhan-sheng-blue electronics ltd, and the results of the tests and comparisons were as follows:
comparing the test results of the rate capacity and the cycle performance under the complete battery: referring to fig. 7, the zinc ion battery manufactured by the present invention still has a high capacity of 67mAh/g after 2453 cycles at a current density of 0.5A/g; in contrast, the zinc-ion battery of comparative example 1 had a cycle number of 1880 and a capacity of 58 mAh/g; the zinc ion battery in comparative example 2 was 128 cycles and had a capacity of 13m Ah/g. Therefore, the comparison between the examples and the comparative examples proves that the zinc ion battery manufactured by the method provided by the invention has excellent cycle life and rate performance, has great significance for the application of the energy storage technology of the zinc ion battery with environmental protection and safety, and has higher practicability.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A zinc ion battery is characterized by comprising a shell injected with electrolyte, and an anode, a diaphragm and a cathode which are sequentially arranged in the shell at intervals, wherein the shell is provided with an upper cover with a pouring gate; the positive pole is in by zinc and stainless steel foil and deposit zinc and stainless steel foil composite coating one side constitute, the grid body coating of middle fretwork that the composite coating is for arranging by a plurality of horizontal poles and a plurality of montants are even crisscross to be constituteed, the composite coating adopts the low temperature to write directly 3D printing technique printing ink and forms, the ink includes N-methyl pyrrolidone and dissolves PC/SiOC combined material, polyvinylidene fluoride and conductive carbon black in the N-methyl pyrrolidone, PC/SiOC combined material is in by porous carbon and interpenetrating silica carbon network on the porous carbon constitutes.
2. The zinc-ion battery of claim 1, wherein the electrolyte is ZnSO 4 Deionized water solution.
3. The zinc-ion battery of claim 1, wherein the separator is a polypropylene separator and the cathode is V 2 O 5 a/C plate.
4. The zinc-ion battery of claim 1, wherein the positive and negative terminals are both copper-based silver-plated alloy.
5. The zinc-ion battery as claimed in claim 1, wherein the middle hollow is a square hollow, the side length of the square hollow is equal to the line width of the horizontal bar and the vertical bar, the horizontal bar and the vertical bar have the same size, and the line width is 400-420 μm.
6. The zinc-ion battery of claim 1, wherein the zinc and stainless steel foils are 0.1mm thick and the composite coating is 500-550 μm thick.
7. A method of making the zinc-ion battery of claim 1, comprising the steps of:
performing ball milling treatment on a PC/SiOC composite material, polyvinylidene fluoride and conductive carbon black, and dissolving the PC/SiOC composite material, polyvinylidene fluoride and conductive carbon black in N-methyl pyrrolidone to obtain an ink composition, wherein the PC/SiOC composite material consists of porous carbon and a silicon-oxygen-carbon network interpenetrating the porous carbon;
removing lumps and large particles in the ink composition by vacuum filtration, and standing for a predetermined time at room temperature to obtain ink;
printing the ink on one surface of zinc and stainless steel foil by using a low-temperature direct-writing 3D printing technology, and drying in vacuum to obtain an anode;
sequentially installing the anode, the diaphragm and the cathode in a shell, and installing an upper cover with a pouring port on the shell;
welding a positive terminal at the upper end of the cathode, welding a negative terminal at the upper end of the anode, and injecting electrolyte from a pouring gate of the upper cover until the electrolyte is fully injected;
and installing a sealing cover at the pouring gate of the upper cover to obtain the zinc ion battery.
8. The method for preparing the zinc-ion battery according to claim 7, wherein the step of printing the ink on one side of zinc and stainless steel foils by using a low-temperature direct-writing 3D printing technology, and preparing the dendrite-free anode of the zinc-ion battery after vacuum drying treatment comprises the following steps:
filling the ink into an injector needle tube connected with a lockable stainless steel blunt nozzle, extruding the ink from the injector needle tube through the lockable stainless steel blunt nozzle, and printing the ink on one surface of zinc and stainless steel foil to obtain an anode of the composite material coating in an uncured state;
and (3) placing the anode of the composite material coating in an uncured state into a vacuum oven, setting the temperature of the vacuum oven to 80 ℃, and keeping the temperature for 12 hours to obtain the dendrite-free anode of the zinc ion battery.
9. The method for preparing the zinc ion battery according to claim 7, wherein the preparation of the PC/SiOC composite material comprises the following steps:
preparation of isoreticular covalently functionalized zirconium-based MOF crystals, namely UiO-66-NH 2 A crystal;
dissolving cetyl trimethyl ammonium bromide in a PDSDA methanol solution in an ultrasonic bath to obtain a PDSDA/CTAB mixed solution; the UiO-66-NH is stirred under magnetic force 2 Dissolving the crystal in methanol to obtain UiO-66-NH 2 A solution;
adding PDSDA/CTAB mixed solution into the UiO-66-NH in an argon atmosphere 2 Stirring the solution at room temperature, then performing argon degassing, sample collection, ethanol washing and vacuum drying after completing the polymerization reaction in MOFs to prepare a UiO-66/PDSDA composition;
the UO-66/PDSDA composition was placed in a tube furnace and subjected to a three-stage pyrolysis process under argon atmosphere: in the first stage, the temperature is raised from 25 ℃ to 400 ℃ at a rate of 2 ℃/min, and then the temperature is maintained at 400 ℃ for two hours; in the second stage, the temperature is increased from 200 ℃ to 800 ℃ at the temperature increase rate of 2 ℃/min, and the temperature is kept at 800 ℃ for four hours; in the third stage, the temperature is reduced from 800 ℃ to room temperature at the temperature reduction rate of 2 ℃/min.
10. The method of claim 7, wherein the UiO-66-NH is present 2 The preparation of the crystal comprises the steps of:
reacting ZrCl 4 And H 2 N-H 2 BDC is dissolved in HCON (CH) at the same concentration of 0.02mol/L to 0.025mol/L 3 ) 2 Then adding hydrochloric acid, hydrochloric acid and HCON (CH) 3 ) 2 The volume ratio of (1: 140) to obtain a mixed solution;
after stirring the mixed solution at room temperature for 30 minutes, the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and heated at 120 ℃ for 10 hours in a hydrothermal manner, after which a yellow powder product was obtained by centrifuging the suspension, which was subsequently washed with absolute ethanol, then transferred to a schlenk flask and dried at ambient temperature to obtain UiO-66-NH 2 And (4) crystals.
CN202210575014.0A 2022-05-25 2022-05-25 Zinc ion battery and preparation method thereof Pending CN114843628A (en)

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