CN115385350B - Preparation method and application of hydroxylated boron alkene material - Google Patents

Preparation method and application of hydroxylated boron alkene material Download PDF

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CN115385350B
CN115385350B CN202211078930.XA CN202211078930A CN115385350B CN 115385350 B CN115385350 B CN 115385350B CN 202211078930 A CN202211078930 A CN 202211078930A CN 115385350 B CN115385350 B CN 115385350B
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hydroxylated
zinc
aqueous solution
chloride aqueous
battery
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CN115385350A (en
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张培新
雍波
马定涛
孙世昌
王艳宜
米宏伟
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Shenzhen University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/023—Boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
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    • 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

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Abstract

The application provides a preparation method of a hydroxylated boron alkene material, which comprises the following steps: preparing metal chloride aqueous solution, including 8-10mol/L zinc chloride aqueous solution, or 2-5mol/L magnesium chloride aqueous solution, or 2-5mol/L ferric chloride aqueous solution; and (3) dropwise adding ultrasonic dispersion of the layered metal boride in water into metal chloride water solution at room temperature, stirring until the color of the system is not changed, centrifuging the obtained reaction material, and then washing with hydrochloric acid for multiple times and washing with water for multiple times to obtain the solid material, namely the hydroxylated boron alkene. The preparation method is simple to operate, is suitable for batch preparation, and has the advantages of high yield, uniform size and good stability of the hydroxylated boron alkene. The application also provides a modified diaphragm modified by the hydroxylation boron alkene, a zinc ion battery and other related applications, and the modified diaphragm can inhibit dendrite growth of the negative electrode of the zinc battery and prolong the cycle life of the battery.

Description

Preparation method and application of hydroxylated boron alkene material
Technical Field
The application relates to the technical field of two-dimensional boron alkene materials, in particular to a preparation method and application of a hydroxylated boron alkene material.
Background
The two-dimensional material has great application prospect in the fields of catalysis, energy storage, electronic information and the like by virtue of the excellent physical and chemical properties. However, as a new member of the two-dimensional material family, boron alkene has been paid attention to because of its characteristics of diversified structures, ultra-high conductivity, adjustable band gap, good thermal stability, etc.
At present, the preparation of the boron alkene mainly comprises a vapor deposition method and a liquid phase stripping method, but the equipment used by the vapor deposition method is expensive, the preparation conditions are harsh, and the prepared product is difficult to strip off from a metal substrate, has low yield, is unfavorable for large-scale preparation and the like; although the liquid phase stripping method is used for preparing the borane, the special structure of the boron is different from the existing two-dimensional material, so that the stripping efficiency of the borane material prepared by the liquid phase stripping method is low (generally not more than 5 percent), and the uniformity of the dimension of the borane material is difficult to control. In addition, the surface of the borane material prepared by the two methods is generally not provided with functional groups, so that the diversified application of the borane material is difficult to expand. Therefore, it is necessary to provide a method for conveniently preparing functionalized borene in a large scale with high yield and enrich the application forms thereof.
Disclosure of Invention
In view of the above, the application provides a preparation method and application of surface functionalized borane. The preparation method is suitable for preparing the borazine in batches, the yield of the borazine is high, and the surface of the obtained borazine is rich in hydroxyl functional groups and can be directly applied in related applications. In particular, the application provides a new application of the hydroxylated boron alkene for modifying the zinc battery diaphragm, which can solve the problem that dendrites of the zinc ion battery are difficult to inhibit.
In a first aspect, the present application provides a method for preparing a hydroxylated borazine material, comprising the steps of:
(1) Adding the layered metal boride into water, and performing ultrasonic dispersion to obtain boron source dispersion;
preparing a metal chloride aqueous solution, wherein the metal chloride aqueous solution comprises 8-10mol/L zinc chloride aqueous solution, 2-5mol/L magnesium chloride aqueous solution or 2-5mol/L ferric chloride aqueous solution;
(2) Dropwise adding the boron source dispersion into the metal chloride aqueous solution at room temperature, and continuously stirring until the color of the system is not changed any more to obtain a reaction material;
(3) Centrifuging the obtained reaction material, collecting solid matters, and sequentially washing the solid matters with hydrochloric acid for multiple times and washing the solid matters with water for multiple times to obtain a solid material, namely the hydroxylated boron alkene material.
In the preparation method provided by the application, lamellar metal boride is taken as a boron source, and ultrasonic dispersion liquid and zinc chloride (ZnCl) with specific concentration are adopted 2 ) Aqueous solution, magnesium chloride (MgCl) 2 ) Aqueous solutions or ferric chloride (FeCl) 3 ) Stirring the aqueous solution for reaction, and etching interlayer metal elements of the layered metal boride by means of complex acid generated by chloric acid hydrolysis to prepare borane; in addition, znCl 2 、FeCl 3 The metal ions in the metal ion-containing layer can be subjected to oxidation-reduction reaction with the interlayer metal layer of the layered metal boride, and can be cooperated with the etching action of the matched acid to remove the interlayer metal element, so that the B layer is left to prepare the borane. The obtained boron alkene is in an electron-deficient state, then hydrochloric acid is used for washing to provide hydrogen ions, boron hydride or surface part hydroxylation boron alkene is easy to form, and then water washing is used for further reaction of the boron hydride alkene and water, so that a surface hydroxylation boron alkene product is finally obtained.
The preparation method has the advantages of low reagent consumption, no need of complex reaction equipment, simple operation, mild conditions, effective removal of interlayer metal elements of the layered metal boride, few metal impurities in the borane, realization of the preparation of the borane, realization of the regulation and control of surface functional groups of the borane, good dispersibility of the obtained hydroxylated borane in water or organic solvents, good preservation stability, and overcoming of the problems of poor stability and difficult preservation of the existing borane materials. Compared with a borane product with no hydroxyl on the surface, which is prepared by a liquid phase stripping method, the stable dispersion time of the borane product in an aqueous solution can be greatly improved.
In an embodiment of the present application, in step (1), the layered metal boride includes, but is not limited to, magnesium diboride (MgB) 2 ) Aluminum diboride (AlB) 2 ) Vanadium diboride (VB) 2 ) Zirconium diboride (ZrB) 2 ) Titanium diboride (TiB) 2 ) And the like. Some prior art adopts layered metal boride such as magnesium diboride and the like as a boron source, and removes interlayer metal ions by adding ion exchange resin or chelating agent to prepare the borane nano-sheet, and the borane prepared by the method is an independent material, so that the yield is improved, but the preparation process is complex, the cost is high, the removal effect of the interlayer metal ions is poor, and the metal impurities are more. The application adopts the metal chloride with specific concentration to effectively remove the interlayer metal ions of the two-dimensional lamellar substances so as to prepare the borane. In some embodiments, the layered metal boride is magnesium diboride or aluminum diboride.
In the step (1), the ultrasonic dispersion is carried out at a power of 400-700W. The higher ultrasonic power is favorable for fully dispersing and generating proper initial stripping of the layered metal boride, and is convenient for subsequent full reaction with metal chloride. In some embodiments, the ultrasonic dispersion is performed at a power of 500-600W. Wherein, the time of ultrasonic dispersion can be adjusted according to the adding amount of the layered metal boride. In some embodiments, the ultrasonic dispersion may be performed for a period of time ranging from 5 to 10 minutes. In the boron source dispersion, the mass ratio of the layered metal boride to water is (40-60) mg/mL, for example, 45, 50, 55 or 60mg/mL, etc.
In the step (1), when the metal chloride aqueous solution is prepared, the metal chloride in a solid state and water may be mixed under stirring. Wherein the stirring speed can be 500-800 rpm, and the stirring time can be 10-30 min. Stirring can be favorable for fully dissolving the metal chloride salt in water, and simultaneously, the heat generated by dissolution is released as soon as possible. Wherein, the aqueous solutions of zinc chloride, magnesium chloride and ferric chloride are strong acid and weak alkali salts, and the concentrations of the zinc chloride, the magnesium chloride and the ferric chloride are controlled in the above range, so that the zinc chloride, the magnesium chloride and the ferric chloride can be fully dissolved, and the aqueous solutions of the zinc chloride, the magnesium chloride and the ferric chloride can be ensured to have enough acidity so as to etch interlayer metal ions of the layered metal boride.
In order to ensure that the layered metal boride can be sufficiently etched by the metal chloride, in step (2), the molar ratio of the mass of the layered metal boride to the magnesium chloride or ferric chloride in the boron source dispersion is controlled to be 20: (2-5) g/mol; the molar ratio of the mass of the layered metal boride in the boron source dispersion to the zinc chloride is 20: (8-10) g/mol. In some embodiments, the volume ratio of the boron source dispersion to the metal chloride aqueous solution is 2:5.
wherein, the time of continuous stirring can be determined according to the color change condition of the system after the boron source dispersion liquid and the metal chloride aqueous solution are added. Generally, when the color of the system solution changes from black to stable brown, interlayer metal ions representing the layered metal boride are substantially extracted. In some embodiments of the application, the duration of stirring is 12 to 24 hours, for example 15 to 20 hours. Wherein the speed of continuous agitation may be 550, 600, 650, 700, 750, or 800 revolutions per minute.
In the step (3), the centrifugation may be performed at a rotational speed of 10000-15000r/min for 15-40 minutes. Hydrochloric acid and the chloride salt contain chloride ions, and the solid matters in the reaction materials in the step (2) are washed by adopting the hydrochloric acid, so that no extra anion impurities are introduced. In some embodiments, the acid used for the acid wash is hydrochloric acid at a concentration of 1 mol/L.
In the step (3), "the solid matter is washed with hydrochloric acid and water for a plurality of times in sequence", specifically comprising: a) Adding hydrochloric acid washing liquid into the solid, shaking for washing, centrifuging at a high speed, and collecting the solid; repeating the washing-centrifuging operation for a plurality of times to obtain a first solid; b) Adding water to the first solid, shaking for washing, centrifuging at a high speed, and collecting the solid; the washing-centrifuging operation is repeated for a plurality of times until the pH of the water washing liquid after centrifuging is neutral, and collecting the solid material. Wherein, the high-speed centrifugation can be carried out for 10-30 minutes at the rotating speed of 10000-12000 r/min.
In some embodiments of the present application, after the step (3), the following step (4) is further included: and (3) freeze-drying the solid material obtained in the step (3) to obtain the dried hydroxylated boron alkene material. Further, the freeze-dried hydroxylated borane material may be dispersed in a solvent to obtain a dispersion of the hydroxylated borane material. The specific post-treatment method of the boron alkene material can be adjusted according to the specific application scene.
The thickness of the hydroxylated boron alkene material prepared by the present application is less than 5nm, for example less than or equal to 4.5nm, or less than or equal to 4nm, or less than or equal to 3.8nm. In some embodiments, the thickness is 0.54nm to 3.8nm. Wherein, the mass content of boron element in the hydroxylation boron alkene material is more than 90%, for example, 95-98%. The content of boron element can be obtained by carrying out energy spectrum analysis on the hydroxylated boron alkene material.
The preparation method provided by the first aspect of the application realizes the preparation of the ultra-stable borane, has simple process and low cost, is easy to realize large-scale production, and has high yield, high purity and good dispersibility of the product. The preparation method avoids the severe condition and complicated preparation process of the existing preparation method, and improves the product quality. The surface of the obtained borane is rich in hydroxyl functional groups, and related applications can be directly carried out.
Zinc battery, especially water system zinc ion battery, has abundant zinc reserves, low cost, good safety and Zn 2+ Zn has the advantages of low oxidation-reduction potential, high theoretical specific capacity and the like, and is favored. At present, the water system zinc ion battery still has the problems of dendrite, dead zinc, side reaction (hydrogen evolution, corrosion, negative products) and the like, especially, in the process of charging and discharging the battery, the intercalation/deintercalation of zinc ions can lead to uneven distribution of an electric field/an ion field, zinc dendrite is easy to generate on the surface of the zinc negative electrode, and the zinc dendrite continuously grows, so that a diaphragm which originally separates the positive electrode from the negative electrode is pierced, and the positive electrode and the negative electrode are in direct contact to cause short circuit of the battery, which severely restricts the application of the zinc battery.
In view of the above, a second aspect of the present application provides a modified separator for a zinc battery, comprising a separator substrate, a modification layer provided on the separator substrate, the modification layer comprising a hydroxylated borane material, the modification layer being provided on a side of the separator substrate facing a negative electrode of the zinc battery. The hydroxylated boron alkene material can be obtained by the preparation method according to the first aspect of the present application, and can also be prepared by other methods.
The hydroxylated boron alkene material has good hydrophilicity and dispersibility, the inventor finds that the hydroxylated boron alkene material also has good zinc affinity, the hydroxylated boron alkene material is arranged on the surface of one side of the diaphragm substrate, which is close to the negative electrode of the zinc battery, the formed modification layer can homogenize the electric field distribution of the negative electrode of the zinc battery, homogenize the ion transmission of the interface between the negative electrode and the electrolyte, and reduce the ion concentration polarization of the interface, so that the homogenized deposition of zinc ions is guided, the growth of zinc dendrites is inhibited, and the cycle life of the zinc battery is prolonged. And the modified layer formed by the hydroxylated boron alkene material also has certain toughness, even if zinc dendrites are formed on the zinc cathode, the zinc dendrites can be prevented from penetrating through the diaphragm base material to reduce the risk of short circuit in the battery, and the safety of the battery is improved. In particular, the hydroxylated borane material prepared by the preparation method of the first aspect of the present application can have better dispersibility on the surface of the diaphragm substrate.
In an embodiment of the present application, the loading of the hydroxylated borazine material in the modified separator may be in the range of 0.5 to 1.5mg/cm 2 . I.e. per cm 2 The mass of the hydroxylated borazine material is 0.5-1.5mg on the membrane substrate. The hydroxylated boron alkene material has proper load capacity on the surface of the diaphragm substrate, and can ensure that the hydroxylated boron alkene material forms a modification layer with certain thickness and compactness, so that current is uniform, zinc ions are conveniently and uniformly deposited, zinc dendrites are effectively prevented from penetrating through the diaphragm, and meanwhile, when the diaphragm with the modification layer on the surface is used in a battery, the internal resistance of the battery is not obviously increased. Specifically, the above-mentioned loading amount may be 0.6, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3 or 1.4mg/cm 2 . In some embodiments, the loading of the hydroxylated borane material in the modified separator may be in the range of 0.8 to 1.2mg/cm 2 。
In an embodiment of the present application, the thickness of the finishing layer is 5 μm to 15 μm. The modification layer with proper thickness can ensure better elasticity/toughness, can effectively prevent the diaphragm from being pierced by zinc dendrites, and can not excessively increase the internal resistance of the battery. Specifically, the thickness of the modification layer may be 6 μm, 7 μm, 8 μm, 9 μm, 9.9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 14.5 μm, or the like. In some embodiments, the thickness of the modifying layer is 5.5 μm to 12 μm.
In general, the separator substrate is a supporting material having a porous structure. Wherein the membrane substrate comprises one or more of a glass fiber membrane, a dust free paper membrane, a ceramic membrane, a polymer membrane (such as a polyolefin membrane), and the like.
In some embodiments of the application, the hydroxylated borazine material is bonded to the membrane substrate by vacuum filtration. Therefore, the bonding force between the hydroxylated boron alkene material and the diaphragm substrate is ensured to be stronger, the modification layer has certain density, the uniformity of zinc ion flow is facilitated, and the growth of zinc dendrites on the surface of the negative electrode is well inhibited. Of course, in other embodiments of the present application, the hydroxylated borane material may also be formed on the separator substrate by coating, dipping, or the like.
The embodiment of the application also provides a preparation method of the modified diaphragm. Specifically, the modified diaphragm can be prepared by the following method:
(1) Preparing a dispersion comprising a finishing layer material and a first solvent, the finishing layer material comprising a hydroxylated borazine material;
(2) And carrying out vacuum suction filtration on the dispersion liquid to the membrane base material so as to enable the hydroxylated boron alkene material to be distributed on the surface of the membrane base material to form a modification layer, and carrying out vacuum drying to obtain the modified membrane with the modification layer on the surface.
The vacuum filtration method can ensure that the material of the modification layer is arranged on the surface of the diaphragm substrate in an oriented way, ensures that the modification layer has certain density, and ensures that the material of the modification layer is tightly combined on the diaphragm substrate without falling off. The modified diaphragm prepared by the method can have a good effect of inhibiting the growth of zinc negative dendrites.
In the step (1), the first solvent may be one or more of N-methylpyrrolidone (NMP), N Dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetone, acetonitrile, ethanol, isopropanol, water, etc. In the dispersion liquid, the mass volume concentration ratio of the material of the modification layer to the first solvent is (0.5-1.0): 1mg/mL. This may facilitate subsequent formation of a modification layer of suitable thickness on the separator substrate. In some embodiments of the application, the dispersion of the finishing layer material is obtained by dispersing the hydroxylated borane material prepared by the preparation method according to the first aspect of the application in a first solvent.
In the embodiment of the application, in the step (2), when the dispersion liquid is vacuum filtered onto the membrane substrate, the side of the membrane substrate, which is to face the negative electrode of the zinc battery, can be upwards. Therefore, the membrane substrate is ensured to be provided with a modified layer with a hydroxylation boron alkene material on the side facing the negative electrode of the zinc battery, so as to play a role in inhibiting the growth of negative electrode zinc dendrite.
In some embodiments of the application, the separator substrate is further soaked with a first solvent prior to vacuum filtering the dispersion to the separator substrate. The soaking can improve the interface property of the diaphragm base material, ensure the full and uniform wettability of the dispersion liquid of the modification layer material on the diaphragm base material, and facilitate the improvement of the good dispersibility of the boron alkene on the diaphragm base material in the later period. Alternatively, the soaking time may be 5-30min, for example 10-20min.
In the step (2), the temperature of the vacuum drying can be 60-70 ℃ and the time is 12-18h.
The embodiment of the application also provides a zinc ion battery, which comprises the modified diaphragm according to the second aspect of the application.
The zinc ion battery adopting the modified diaphragm has the advantages that zinc dendrites are not easy to grow on the negative electrode, and the zinc dendrites are not easy to pierce the battery diaphragm to cause internal short circuit, so that the zinc ion battery has good cycle performance and safety performance.
Wherein the zinc ion battery further comprises a positive electrode, a negative electrode and an electrolyte, the modified diaphragm is arranged between the positive electrode and the negative electrode, and the modification layer is positioned on one side of the modified diaphragm close to the negative electrode (namely, close to the negative electrode). And the electrolyte infiltrates the modified diaphragm, the anode and the cathode. The zinc ion battery can be a rechargeable zinc ion battery, and can be a symmetrical battery, a half battery or a full battery. The shape of the zinc ion battery is not limited in the application.
The present application is not particularly limited to the assembly of the zinc ion battery, and may be carried out by an assembly process known to those skilled in the art. In some embodiments, the zinc-ion battery can be prepared by the following method: and sequentially stacking the positive electrode, the diaphragm and the negative film to form a battery core, accommodating the battery core in a battery shell, injecting electrolyte, and sealing the battery shell to obtain the zinc ion battery. In general, after the preparation of the zinc ion battery is completed, the electrochemical performance test is performed after standing for 6 to 8 hours.
Among them, the negative, positive and electrolyte are all conventional choices in the battery field. For example, a positive electrode generally includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector. The positive current collector is generally carbon cloth, stainless steel foil, copper foil, titanium foil or foam nickel; the positive electrode active material layer generally contains a positive electrode active material, a binder, and a conductive agent; the positive electrode active material may be an oxide, fluoride, sulfide or a composite thereof, or other materials, or the like. In some embodiments, the negative electrode is a zinc sheet.
In some embodiments of the application, the electrolyte is an aqueous electrolyte, in particular an aqueous solution containing a Zn salt. Because the electrolyte of the zinc ion battery adopts water as a solvent, the zinc ion battery has higher ionic conductivity and can be rapidly charged and discharged, so that the zinc ion battery has the advantages of high power density, long cycle life, capacity fading reduction and the like. In some embodiments, the electrolyte is an aqueous solution of zinc sulfate, or a mixed aqueous solution of zinc sulfate and manganese sulfate.
The embodiment of the application also provides application of the hydroxylated boron alkene material in a zinc ion battery.
Wherein, the hydroxylation boron alkene material can be used on the surface of a diaphragm and/or the surface of a negative electrode of a zinc ion battery. Thus, zinc dendrite growth on the surface of the negative electrode can be inhibited by the hydroxylated boron alkene material, and zinc dendrite penetration of a diaphragm and the like can be prevented. The zinc ion battery with the hydroxylated boron alkene material has good cycle performance and safety performance.
Drawings
FIG. 1 summarizes X-ray Diffraction (XRD) spectra of a hydroxylated borane material prepared according to example 1 of the present application and a magnesium diboride as a preparation starting material.
FIG. 2 is a Fourier transform infrared (Fourier Transform infrared spectroscopy, FTIR) spectrum of a hydroxylated borane material prepared according to example 1 of the present application.
Fig. 3 is a field emission scanning electron microscope (Field scanning electron microscope, FSEM) photograph of the hydroxylated borane material prepared according to example 1 of the present application.
FIG. 4 is an atomic force microscope (Atomic Force Microscope, AFM) image and a layer thickness profile of the hydroxylated borane material of example 1 of the present application.
FIG. 5 is a photograph of the Tyndall effect of an aqueous dispersion of a hydroxylated borane material in example 1 of the present application.
Figure 6 summarizes the XRD patterns of the hydroxylated borane materials produced in examples 2-4.
FIG. 7 summarizes the XRD patterns of the hydroxylated borane materials produced in examples 5-7.
FIG. 8 is an AFM image of the hydroxylated borane material of example 8 of the present application and a layer thickness profile thereof.
Fig. 9 is a photograph comparison of the separator before and after modification with the hydroxylated borazine material of example 1.
Fig. 10 is a time-voltage plot of zinc deposition/stripping test for a symmetrical cell assembled with a separator modified with a boronated material and a symmetrical cell assembled with an unmodified separator of example 1.
FIG. 11 is a scanning electron microscope image of the surface of a zinc negative electrode after cyclic testing of a symmetrical battery assembled with a separator modified with a boronated material of example 1 and a symmetrical battery assembled with an unmodified separator.
Detailed Description
The present application will be further described with reference to specific examples. It will be appreciated by those skilled in the art that the embodiments described below are some, but not all, of the embodiments of the present application and are merely illustrative of the present application and should not be construed as limiting the scope of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application. Unless otherwise specified, the raw materials used in the examples of the present application are all commercially available.
Example 1
Mixing 100mg of magnesium diboride with 2mL of deionized water at room temperature, and performing ultrasonic treatment at 600W for 5 minutes to obtain magnesium diboride dispersion; meanwhile, 5mL of zinc chloride solution with the concentration of 10mol/L is prepared, and the mixture is stirred for 10 minutes at the rotating speed of 500 r/min; the above magnesium diboride dispersion was added dropwise to a zinc chloride solution (added in a plurality of portions over about 2 minutes), and after the completion of the addition, stirring was continued at room temperature for 15 hours, and the stirring was stopped when the color of the system solution was observed to change from black to brown, to obtain a reaction mass. Then, washing the reaction material with 5mL of hydrochloric acid with the concentration of 1mol/L for 3 times, and washing with deionized water for multiple times until the pH value of the washing liquid is neutral; finally, drying for 20 hours by a freeze dryer to obtain the hydroxylated boron alkene material. The resulting hydroxylated borane material may be dispersed in water or an organic solvent such as NMP.
FIG. 1 summarizes XRD spectra of the hydroxylated borane material prepared according to example 1 of the present application and of the magnesium diboride as the preparation starting material. As can be seen from FIG. 1, magnesium diboride is processed by the method of example 1 from MgB 2 The evolution of the multimodal of (2) into a monomodal of boranes, which indicates MgB 2 The etching of the interlayer metal element is completed, and the reaction is more complete.
FIG. 2 is an infrared spectrum of the hydroxylated borane material of example 1 of the present application. Wherein 1616cm -1 The peak at which corresponds to the B-H-B bond, 638cm -1 The peak at which corresponds to B-OH, i.e., hydroxylated borane, in combination with the XRD pattern of fig. 1, may indicate that successful etching of the present application yields a material indicating hydroxylated borane.
Fig. 3 and 4 are FSEM photographs and AFM characterization results, respectively, of the hydroxylated borane material prepared according to example 1 of the present application. From the pictures, the hydroxylated boron alkene material prepared by the method is in a sheet structure, has good dispersibility, does not form agglomerates, and also verifies the feasibility of the preparation method. Furthermore, as can be seen from FIG. 4, the thickness of the resulting hydroxylated borane material was 3.64nm.
The hydroxylated borane material prepared in example 1 was dispersed in deionized water to give a hydroxylated borane dispersion. FIG. 5 is a photograph of the tyndall effect of the hydroxylated borane dispersion. As can be seen from fig. 5, the hydroxylated boranes have good dispersibility in water and can form transparent colloid.
Example 2
Mixing 100mg of magnesium diboride with 2mL of deionized water at room temperature, and performing ultrasonic treatment at 550W for 5 minutes to obtain magnesium diboride dispersion; meanwhile, 5mL of magnesium chloride solution with the concentration of 2mol/L is prepared, and the mixture is stirred for 10 minutes at the rotating speed of 800 r/min; the above magnesium diboride dispersion was added dropwise to a magnesium chloride solution (addition was completed in a plurality of times, about 2 minutes), and stirring was continued at room temperature after completion of the addition, and when the color of the system solution was observed to change from black to brown, the stirring was stopped (total stirring time was about 24 hours), to obtain a reaction mass. Then, washing the reaction material with 5mL of hydrochloric acid with the concentration of 1mol/L for 3 times, and washing with deionized water for multiple times until the pH value of the washing liquid is neutral; finally, drying for 20 hours by a freeze dryer to obtain the hydroxylated boron alkene material.
Example 3
The preparation method of the hydroxylated boron alkene material in the embodiment 2 is different in that: the concentration of the magnesium chloride solution was 5mol/L.
Example 4
The preparation method of the hydroxylated boron alkene material in the embodiment 2 is different in that: the concentration of the magnesium chloride solution was 3.5mol/L.
Example 5
Mixing 100mg of magnesium diboride with 2mL of deionized water at room temperature, and performing ultrasonic treatment at 600W for 5 minutes to obtain magnesium diboride dispersion; meanwhile, preparing 5mL of ferric chloride solution with the concentration of 5mol/L, and stirring for 10 minutes at the rotating speed of 500 r/min; the above magnesium diboride dispersion was added dropwise to the ferric chloride solution (addition was completed in a plurality of times, about 2 minutes), and stirring was continued at room temperature after the completion of the addition, and when the color of the system solution was observed to change from black to brown, the stirring was stopped (total stirring time was about 24 hours), to obtain a reaction mass. Then, washing the reaction material with 5mL of hydrochloric acid with the concentration of 1mol/L for 3 times, and washing with deionized water for multiple times until the pH value of the washing liquid is neutral; finally, drying for 20 hours by a freeze dryer to obtain the hydroxylated boron alkene material.
Example 6
The preparation method of the hydroxylated boron alkene material in the embodiment 5 is different in that: the concentration of the ferric chloride solution was 3.5mol/L.
Example 7
The preparation method of the hydroxylated boron alkene material in the embodiment 5 is different in that: the concentration of the ferric chloride solution was 2mol/L.
Figure 6 summarizes the XRD patterns of the hydroxylated borane materials produced in examples 2-4. FIG. 7 summarizes the XRD patterns of the hydroxylated borane materials produced in examples 5-7. As can be seen from FIGS. 6 to 7, the magnesium chloride solution and the ferric chloride solution with different concentrations according to the present application can be prepared from MgB as in example 1 2 The evolution of the multimodal of (2) into a monomodal of boranes, which indicates MgB 2 The etching of the interlayer metal element is completed, and the reaction is more complete.
Example 8
Mixing 120mg of aluminum diboride with 2mL of deionized water at room temperature, and performing ultrasonic treatment at 550W for 5 minutes to obtain an aluminum diboride dispersion; meanwhile, 5mL of ferric chloride solution with the concentration of 4mol/L is prepared, and the mixture is stirred for 10 minutes at the rotating speed of 500 r/min; the above aluminum diboride dispersion was added dropwise to the ferric chloride solution (addition was completed in a plurality of times, about 2 minutes), and stirring was continued at room temperature after completion of the addition, and when the color of the system solution was observed to change from black to brown, the stirring was stopped (total stirring time was about 19 hours), to obtain a reaction mass. Then, washing the reaction material with 5mL of hydrochloric acid with the concentration of 1mol/L for 3 times, and washing with deionized water for multiple times until the pH value of the washing liquid is neutral; finally, drying for 20 hours by a freeze dryer to obtain the hydroxylated boron alkene material.
FIG. 8 is an AFM image of the hydroxylated borane material of example 8 and its layer thickness profile. As can be seen from fig. 8, the hydroxylated borazine material is in the form of flakes having a thickness of about 4.3nm.
Application examples
The hydroxylated boron alkene material prepared by the embodiment of the application is used for modifying the zinc battery diaphragm. Illustratively, a modified separator is prepared comprising the steps of:
1) The hydroxylated borane material prepared in example 1 was added to NMP solvent and dispersed ultrasonically at a power of 500W for 40 minutes to give a borane dispersion with a concentration of 1 mg/mL; soaking a glass fiber diaphragm in NMP solvent for 10-20 minutes;
2) And then vacuum-filtering the above-mentioned boron alkene dispersion liquid on a glass fiber diaphragm so as to enable the hydroxylated boron alkene material to be distributed on the surface of the glass fiber diaphragm to form a modification layer, and finally vacuum-drying at 65 ℃ for 16 hours to obtain a modified diaphragm with the modification layer on the surface (as shown in figure 9). As can be seen from fig. 9, after the surface of the glass fiber diaphragm is modified by the hydroxylated boron alkene material, a modification layer with deeper gray scale is formed on the surface of the glass fiber diaphragm. The loading of the hydroxylated boron alkene material in the obtained modified membrane is 1mg/cm 2 The thickness of the finishing layer is about 11.1 μm.
A method for preparing a zinc ion battery comprising the steps of: two zinc sheets are adopted as an anode and a cathode respectively, and are stacked with the modified diaphragm, and the modified diaphragm is arranged between the two zinc sheets to obtain a battery cell; the cell was housed in a battery case, and an electrolyte (specifically, 120. Mu.L of zinc sulfate solution having a concentration of 2 mol/L) was injected, and then the battery case was sealed to obtain a CR2032 type symmetrical coin cell. The symmetrical cell is designated S1.
In order to highlight the beneficial effects of the application, a CR2032 symmetrical button cell is also assembled by adopting an unmodified glass fiber diaphragm and a zinc sheet and is marked as D1. After the batteries are assembled, the batteries are stood for 6-8 hours and then subjected to electrochemical performance test.
The symmetrical batteries S1 and D1 are set at 5 mA.cm -2 And a current density of 1 mAh.cm -2 The electrochemical deposition/stripping cycle performance test was performed at the surface capacity of (c). Fig. 10 is a graph comparing the time-voltage curves obtained. It can be seen from FIG. 10 that the cycle life of the symmetrical cell D1 does not exceed 450h, while the cycle life of the symmetrical cell S1 can exceed 2000h, and the polarization voltage is only 66mVThe polarization voltage is up to 100mV when the voltage is smaller than 400h compared with the S1 battery, and short circuit occurs, so that the cycling stability of the zinc symmetrical battery S1 is obviously improved. This demonstrates that the separator with the hydroxylated borane modification is advantageous for achieving uniform deposition of zinc, thereby achieving the effects of inhibiting zinc dendrites, preventing the zinc dendrites from piercing the separator, and extending the cycle life of the battery. After that, the cell was disassembled and the separated zinc negative electrode was subjected to FSEM characterization, and the result is shown in fig. 11. As can be seen from fig. 11, the battery assembled with the unmodified separator found many dendrites of zinc on the surface of the negative electrode after the cyclic test, while the battery assembled with the modified separator exhibited a smooth and dense deposition layer on the surface of the negative electrode after the cyclic test, which indicates that the modified separator effectively inhibited the growth of zinc dendrites on the surface of the negative electrode.
In addition, the hydroxylated borane materials prepared in examples 2-8 were also used to prepare modified separators and assembled into symmetrical zinc cells, and the resulting symmetrical cells were designated S2, S3, S4, S5, S6, S7 and S8, respectively. Wherein, at 5 mA.cm -2 And a current density of 1 mAh.cm -2 The cycle life of the batteries S2-S7 can be more than 1000 hours, and the cycle life of the battery S8 is more than 800 hours, which is much longer than that of the D1 battery.
The above examples merely represent a few exemplary embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, and these variations and modifications are within the scope of the application.

Claims (4)

1. The preparation method of the hydroxylated boron alkene material is characterized by comprising the following steps of:
(1) Adding the layered metal boride into water, and performing ultrasonic dispersion to obtain boron source dispersion;
preparing a metal chloride aqueous solution, wherein the metal chloride aqueous solution comprises 8-10mol/L zinc chloride aqueous solution, 2-5mol/L magnesium chloride aqueous solution or 2-5mol/L ferric chloride aqueous solution;
(2) Dropwise adding the boron source dispersion into the metal chloride aqueous solution at room temperature, and continuously stirring until the color of the system is not changed any more to obtain a reaction material;
(3) Centrifuging the obtained reaction material, collecting solid matters, and sequentially washing the solid matters with hydrochloric acid for multiple times and washing the solid matters with water for multiple times to obtain a solid material, namely the hydroxylated boron alkene material.
2. The method of making according to claim 1, wherein the layered metal boride comprises one or more of magnesium diboride, aluminum diboride, vanadium diboride, zirconium diboride, titanium diboride.
3. The method of claim 1, wherein in step (1), the ultrasonic dispersion is performed at a power of 400 to 700W.
4. The method of claim 1, wherein in step (2), the molar ratio of mass of layered metal boride to magnesium chloride or ferric chloride in the boron source dispersion is 20: (2-5) g/mol; the molar ratio of the mass of the layered metal boride in the boron source dispersion to the zinc chloride is 20: (8-10) g/mol.
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