CN115385350A - Preparation method and application of hydroxylated boron alkene material - Google Patents

Preparation method and application of hydroxylated boron alkene material Download PDF

Info

Publication number
CN115385350A
CN115385350A CN202211078930.XA CN202211078930A CN115385350A CN 115385350 A CN115385350 A CN 115385350A CN 202211078930 A CN202211078930 A CN 202211078930A CN 115385350 A CN115385350 A CN 115385350A
Authority
CN
China
Prior art keywords
zinc
boron
aqueous solution
diaphragm
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211078930.XA
Other languages
Chinese (zh)
Other versions
CN115385350B (en
Inventor
张培新
雍波
马定涛
孙世昌
王艳宜
米宏伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen University
Original Assignee
Shenzhen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen University filed Critical Shenzhen University
Priority to CN202211078930.XA priority Critical patent/CN115385350B/en
Publication of CN115385350A publication Critical patent/CN115385350A/en
Application granted granted Critical
Publication of CN115385350B publication Critical patent/CN115385350B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

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

Description

Preparation method and application of hydroxylated boron alkene material
Technical Field
The application relates to the technical field of two-dimensional borane material, in particular to a preparation method and application of a hydroxylated borane 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 excellent physical and chemical properties. However, boron alkene has attracted much attention as a new member of a two-dimensional material family due to its characteristics of diversified structures, ultrahigh conductivity, adjustable band gap, good thermal stability, and the like.
At present, the preparation of the borane mainly comprises a vapor deposition method and a liquid phase stripping method, but the vapor deposition method has expensive equipment and harsh preparation conditions, and the prepared product is difficult to strip from a metal substrate, has low yield, is not beneficial to large-scale preparation and the like; although the liquid phase stripping method is used for preparing the boron-containing alkene, the boron-containing alkene is different from the existing two-dimensional material due to the special structure of boron, so that the stripping efficiency of the boron-containing alkene material prepared by the liquid phase stripping method is low (generally not more than 5 percent), and the size uniformity of the boron-containing alkene material is difficult to control. Moreover, the surface of the boron alkene materials prepared by the two methods usually has no functional groups, so that the diversified application of the boron alkene materials is difficult to expand. Therefore, it is necessary to provide a method for conveniently preparing functionalized borane with high yield and large scale, and enrich the application forms thereof.
Disclosure of Invention
In view of this, the present application provides a preparation method and application of surface functionalized borane. The preparation method is suitable for preparing the borane in batches, the yield of the borane is high, and the surface of the prepared borane is rich in hydroxyl functional groups and can be directly subjected to related application. In particular, the application provides a new application of the hydroxyl boron alkene for modifying the zinc battery diaphragm, which can solve the problem that the dendrite of the zinc ion battery is difficult to inhibit.
In a first aspect, the present application provides a method for preparing a hydroboracene material, comprising the steps of:
(1) Adding the layered metal boride into water, and performing ultrasonic dispersion to obtain a boron source dispersion liquid;
preparing a metal chloride aqueous solution, wherein the metal chloride aqueous solution comprises a zinc chloride aqueous solution with the concentration of 8-10mol/L, or a magnesium chloride aqueous solution with the concentration of 2-5mol/L, or a ferric chloride aqueous solution with the concentration of 2-5 mol/L;
(2) At room temperature, dropwise adding the boron source dispersion liquid into the metal chloride aqueous solution, and continuously stirring until the system color does not change any more, so as to obtain a reaction material;
(3) And centrifuging the obtained reaction material, collecting a solid, and sequentially washing the solid with hydrochloric acid and water for multiple times to obtain the solid material, namely the boron oxide hydride material.
In the preparation method provided by the application, the layered metal boride is used as a boron source, and the ultrasonic dispersion liquid of the layered metal boride and zinc chloride (ZnCl) with specific concentration are mixed 2 ) Aqueous solution, magnesium chloride (MgCl) 2 ) Aqueous solution or ferric chloride (FeCl) 3 ) Stirring the aqueous solution for reaction, and etching the interlaminar metal elements of the layered metal boride by virtue of a complex acid generated by chloride hydrolysis to prepare the borane; furthermore, znCl 2 、FeCl 3 The metal ions in the boron oxide can generate oxidation-reduction reaction with the interlaminar metal layer of the layered metal boride, and can be cooperated with the etching action of the complex acid to remove interlaminar metal elements, and a B layer is left to prepare the boron alkene. The obtained borolene is in an electron-deficient state, then hydrochloric acid is used for acid washing to provide hydrogen ions, borolene hydride or surface partial hydroxylated borolene is easy to form, and the borolene hydride and water can further react through water washing to finally obtain a surface hydroxylated borolene product.
The preparation method has the advantages of low reagent cost, no need of complex reaction equipment, simple operation, mild conditions, effective realization of removal of interlayer metal elements of the layered metal boride, less metal impurities in the borane, realization of regulation and control of surface functional groups of the borane while almost realizing the preparation of the borane, good dispersibility of the obtained hydroxylated borane in water or organic solvents, good storage stability and overcoming of the problems of poor stability and difficult storage of the existing borane materials. Compared with a boron alkene product prepared by a liquid phase stripping method and having no hydroxyl on the surface, the stable dispersion time of the boron alkene product in an aqueous solution can be greatly prolonged.
In the embodiments 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. In the prior art, layered metal borides such as magnesium diboride and the like are used as a boron source, and the boron alkene nanosheets are prepared by adding ion exchange resin or chelating agent to remove interlayer metal ions. The application adopts metal chloride with specific concentration to effectively remove interlayer metal ions of the two-dimensional layered substances so as to prepare the boron alkene. 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 beneficial to fully dispersing the layered metal boride and generating proper initial stripping, and is convenient for fully reacting with the metal chloride salt subsequently. In some embodiments, the ultrasonic dispersion is performed at a power of 500-600W. Wherein the proceeding time of the ultrasonic dispersion can be adjusted according to the addition amount of the layered metal boride. In some embodiments, the ultrasonic dispersion may be performed for a time period of 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 60 mg/mL.
In the step (1), when preparing the aqueous solution of the metal chloride salt, the solid metal chloride salt and water may be mixed under stirring. Wherein, the stirring speed can be 500-800 r/min, and the stirring time can be 10-30 min. The stirring can be beneficial to fully dissolving the metal chloride in the water, and simultaneously, the heat generated by the dissolution can be released as soon as possible. Wherein, the water solution of zinc chloride, magnesium chloride and ferric chloride is strong acid weak base salt, and the concentration of the zinc chloride, the magnesium chloride and the ferric chloride is controlled in the range, so that the zinc chloride, the magnesium chloride and the ferric chloride can be fully dissolved, and the water solution of the zinc chloride, the magnesium chloride and the ferric chloride can be ensured to have enough acidity so as to etch away interlayer metal ions of the layered metal boride.
In order to ensure that the layered metal boride can be fully etched by the metal chloride, in the step (2), the molar ratio of the mass of the layered metal boride to the magnesium chloride or the ferric chloride in the boron source dispersion liquid 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 liquid to the zinc chloride is 20: (8-10) g/mol. In some embodiments, the volume ratio of the boron source dispersion to the aqueous metal chloride salt solution is from 2:5.
wherein, the time of the 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, the interlayer metal ions in the layered metal boride are substantially removed. In some embodiments of the present application, the duration of the continuous stirring is 12 to 24 hours, such as 15 to 20 hours. Wherein the continuous stirring speed may be 550, 600, 650, 700, 750 or 800 revolutions per minute.
In the step (3), the centrifugation can be carried out for 15-40 minutes at the rotating speed of 10000-15000 r/min. And (3) the hydrochloric acid and the chloride salt are the same as the chloride ions, and the solid matters in the reaction materials in the step (2) are washed by the hydrochloric acid without introducing additional anion impurities. In some embodiments, the acid used for acid washing is hydrochloric acid at a concentration of 1 mol/L.
In the step (3), "hydrochloric acid washing and water washing are sequentially performed on the solid substance for multiple times", specifically including: a) Adding a hydrochloric acid washing solution into the solid matter, shaking for washing, then centrifuging at a high speed, and collecting the solid matter; repeating the washing-centrifuging operation for a plurality of times to obtain a first solid; b) Adding water into the first solid, shaking for washing, then centrifuging at a high speed, and collecting the solid; repeating the washing-centrifuging operation for multiple times until the pH of the water washing solution after centrifugation 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 (4) freeze-drying the solid material obtained in the step (3) to obtain a dried boron oxide hydride alkene material. Further, the freeze-dried hydroboracene material may be dispersed in a solvent to obtain a dispersion of the hydroboracene material. The specific post-treatment method of the borane material can be adjusted according to the specific application scene.
The thickness of the hydroboracene material produced herein is less than 5nm, such as 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 between 0.54nm and 3.8nm. Wherein, in the hydroxyl boron alkene material, the mass content of boron element is more than 90%, for example 95-98%. The content of the boron element can be obtained by performing 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 ultrastable borane, has the advantages of simple process, low cost, easy realization of large-scale production, high yield, high purity and good dispersibility of the product. The preparation method avoids the harsh conditions and complex 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 can be directly applied to related applications.
Zinc battery, especially water system zinc ion battery, has the advantages of rich zinc storage, low cost, good safety and Zn 2+ The method has the advantages of low oxidation-reduction potential of Zn, high theoretical specific capacity and the like, and is favored. At present, the problems of dendritic crystals, dead zinc, side reactions (hydrogen evolution, corrosion, negative products) and the like still exist in the water system zinc ion battery, particularly, the zinc ion is embedded/de-embedded in the battery charge-discharge cycle process, so that the electric field/ion field distribution is not uniform, zinc dendritic crystals are easily generated on the surface of the zinc cathode, and the zinc dendritic crystals continuously grow to cause the most serious problemAnd then the diaphragm which originally separates the anode and the cathode is punctured, so that the anode and the cathode are directly contacted to cause the short circuit of the battery, and the application of the zinc battery is seriously restricted.
In view of this, the second aspect of the present application provides a modified separator for a zinc battery, including a separator substrate, and a modification layer disposed on the separator substrate, where the modification layer includes a hydroxlated boron-ene material, and a side of the separator substrate facing a negative electrode of the zinc battery is provided with the modification layer. The preparation method of the hydroboracene material can be used for preparing the hydroboracene material according to the first aspect of the present application, and can also be used for preparing the hydroboracene material by other methods.
The hydroxylated boron alkene material has good hydrophilicity and dispersibility, the applicant 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, close to the negative electrode of the zinc battery, of the diaphragm substrate, the modification layer formed by the hydroxylated boron alkene material can homogenize electric field distribution of the negative electrode of the zinc battery, homogenize ion transmission of the interface between the negative electrode and electrolyte, and reduce ion concentration polarization of the interface, so that zinc ion homogenization deposition is guided, zinc dendrite growth is inhibited, and the cycle life of the zinc battery is prolonged. And, the modification layer that the boron alkene material of hydroxylation formed still has certain toughness, even formed zinc dendritic crystal at the zinc negative pole, can prevent that zinc dendritic crystal from impaling the diaphragm substrate and reduce the risk of short circuit in the battery, has promoted the security of battery. In particular, the boron hydride alkene hydroxylation material prepared by the preparation method of the first aspect of the application can have better dispersibility on the surface of the diaphragm substrate.
In the embodiment of the application, the load amount of the boron hydride material in the modified diaphragm can be 0.5-1.5mg/cm 2 . I.e. per cm 2 The mass of the hydroboracene material on the diaphragm base material of (2) is 0.5-1.5mg. The hydroxyl boron alkene material has suitable load capacity on the surface of the diaphragm substrate, can ensure that the modification layer with certain thickness and compactness is formed, so that the current is uniform, the zinc ions are conveniently and uniformly deposited, the diaphragm is effectively prevented from being pierced by the zinc dendrites, and meanwhile, when the diaphragm with the modification layer on the surface is used in the battery, the internal resistance of the battery can not be obviously increased. Specifically, the above loading amount may be 0.6, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3 or1.4mg/cm 2 . In some embodiments, the modified membrane may have a boron-ene-hydroxide material loading of 0.8 to 1.2mg/cm 2 。
In the embodiment of the application, the thickness of the modification layer is 5-15 μm. The modification layer with proper thickness can ensure better elasticity/toughness, and can effectively prevent the separator from being pierced by zinc dendrite without excessively increasing 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 modifying layer has a thickness of 5.5 μm to 12 μm.
Generally, 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 present application, the hydroxponene material is bonded to the membrane substrate by vacuum filtration. Therefore, the bonding force between the hydroxyl boron alkene material and the diaphragm substrate can be ensured to be stronger, the modification layer has certain density, the zinc ion flow is more uniform, and the growth of zinc dendrites on the surface of the negative electrode is better inhibited. Of course, in other embodiments of the present application, the boron-hydride-alkene material may 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 membrane can be prepared by the following method:
(1) Preparing a dispersion liquid containing a modification layer material and a first solvent, wherein the modification layer material comprises a boron-ene-hydroxide material;
(2) And carrying out vacuum filtration on the dispersion liquid on the diaphragm substrate so as to enable the boron-alkene-hydroxide material to be distributed on the surface of the diaphragm substrate to form a modification layer, and then carrying out vacuum drying to obtain the modified diaphragm with the modification layer on the surface.
By means of the vacuum filtration method, the modification layer material can be ensured to be directionally distributed on the surface of the diaphragm base material, the modification layer has certain density, and the modification layer material is ensured to be tightly combined on the diaphragm base material without falling off. The modified diaphragm prepared by the method has a good effect of hindering dendritic crystal growth of the zinc cathode.
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, and the like. In the dispersion liquid, the mass volume concentration ratio of the modification layer material to the first solvent is (0.5-1.0): 1mg/mL. This facilitates subsequent formation of a finishing layer of suitable thickness on the membrane substrate. In some embodiments of the present application, the dispersion of the modification layer material is obtained by dispersing the boron-oxide-hydride material prepared by the preparation method of the first aspect of the present application into a first solvent.
In the embodiment of the application, in the step (2), when the dispersion liquid is vacuum filtered onto the diaphragm substrate, the side of the diaphragm substrate to be faced to the negative electrode of the zinc battery can be faced upwards. Therefore, the modification layer with the hydroxyl boron alkene material is formed on the negative electrode side of the zinc battery facing the diaphragm base material, so that the function of inhibiting the growth of negative electrode zinc dendrites is exerted.
In some embodiments of the present application, the membrane substrate is further soaked with a first solvent before the dispersion is vacuum filtered to the membrane substrate. The soaking can improve the property of the diaphragm base material to the interface, ensure the sufficient and uniform wettability of the dispersion liquid of the modification layer material to 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.
Embodiments of the present application also provide a zinc ion battery comprising a modified separator as described in the second aspect of the present 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 diaphragm of the battery to cause internal short circuit, so that the zinc ion battery has good cycle performance and safety performance.
The zinc ion battery further comprises a positive electrode, a negative electrode and 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 positive electrode and the negative electrode. The zinc ion battery may be a rechargeable zinc ion battery, and may be a symmetrical battery, a half battery or a full battery. The shape of the zinc-ion battery is not limited in the present application.
The assembly of the zinc ion battery is not particularly limited, and an assembly process known to those skilled in the art may be used. In some embodiments, the zinc-ion battery can be prepared by: and (3) sequentially stacking the positive electrode, the diaphragm and the negative film to form a battery cell, accommodating the battery cell in a battery shell, injecting electrolyte, and sealing the battery shell to obtain the zinc ion battery. Generally, after the zinc ion battery is prepared, the electrochemical performance test is carried out after standing for 6 to 8 hours.
Wherein, the negative film, the positive film and the electrolyte are all conventional choices in the battery field. For example, the 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 foamed nickel and the like; 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, etc. In some embodiments, the negative electrode is a zinc sheet.
In some embodiments of the present application, the electrolyte is an aqueous electrolyte, in particular an aqueous solution containing a Zn salt. The electrolyte of the zinc ion battery adopts water as a solvent, has higher ionic conductivity, can be charged and discharged quickly, and has the advantages of high power density, long cycle life, reduced capacity attenuation and the like. In some embodiments, the electrolyte is an aqueous solution of zinc sulfate, or a mixed aqueous solution containing zinc sulfate and manganese sulfate.
The embodiment of the application also provides application of the hydroxylated boron alkene material in a zinc ion battery.
The hydroxylated boron alkene material can be applied to the surface of a diaphragm and/or the surface of a negative electrode of the zinc ion battery. This makes it possible to suppress the growth of zinc dendrites on the surface of the negative electrode and to prevent the zinc dendrites from penetrating the separator or the like by means of the hydroxylated boron alkene material. The zinc ion battery with the hydroxylated boron alkene material can have good cycle performance and safety performance.
Drawings
FIG. 1 summarizes the X-ray Diffraction (XRD) spectra of the hydroxylated boronized olefin material prepared in example 1 of the present application and the preparation of the starting material, magnesium diboride.
FIG. 2 is a Fourier Transform infrared spectroscopy (FTIR) spectrum of a hydroboracene material prepared in example 1 of the present application.
FIG. 3 is a Field emission scanning electron microscope (FSEM) photograph of the hydroxylated borane material prepared in example 1 of the present application.
FIG. 4 is an Atomic Force Microscope (AFM) image and a layer thickness height image of a hydroboracene material obtained in example 1 of the present application.
FIG. 5 is a photograph of the Tyndall effect of an aqueous dispersion of a hydroxaldehyde material in example 1 of the present application.
FIG. 6 summarizes XRD patterns of the borolene hydroxylate materials prepared in examples 2-4.
FIG. 7 summarizes the XRD patterns of the boroxine materials prepared in examples 5-7.
FIG. 8 is an AFM image of a boroxine material produced by example 8 of the present application and a layer thickness height map thereof.
FIG. 9 is a photograph comparing before and after the diaphragm was modified with the hydroboracene material of example 1.
Fig. 10 is a time-voltage plot of zinc deposition/peel tests for a symmetric cell assembled with the modified hydroboracene material separator of example 1 versus a symmetric cell assembled with the unmodified separator.
Fig. 11 is a scanning electron microscope image of the surface of a zinc negative electrode after a cycle test of a symmetric battery assembled by using the separator modified by the hydroxaborone material in example 1 and a symmetric battery assembled by using an unmodified separator.
Detailed Description
The present disclosure is further illustrated with reference to the following specific examples. It will be understood by those skilled in the art that the following examples, which are included as part of the present application and not all of the present application, are illustrative of the present application and should not be taken as limiting the scope of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. Unless otherwise specified, the raw materials used in the examples of the present application are all commercially available products.
Example 1
Mixing 100mg of magnesium diboride with 2mL of deionized water at room temperature, and carrying out ultrasonic treatment for 5 minutes at the power of 600W to obtain a magnesium diboride dispersion liquid; meanwhile, 5mL of zinc chloride solution with the concentration of 10mol/L is prepared and stirred for 10 minutes at the rotating speed of 500 r/min; and (3) dropwise adding the magnesium diboride dispersion into a zinc chloride solution (adding for multiple times, wherein the adding is finished within about 2 minutes), continuously stirring at room temperature for 15 hours after the dropwise adding is finished, and stopping stirring when the color of the system solution is observed to be changed from black to brown during the stirring, thus obtaining a reaction material. Then, washing the reaction materials by 5mL of hydrochloric acid with the concentration of 1mol/L for 3 times, and then washing by deionized water for multiple times until the pH value of the water washing liquid is neutral; and finally drying for 20 hours by using a freeze dryer to obtain the hydroxylated boron alkene material. The resulting hydroboracene material may be dispersed in water or an organic solvent such as NMP.
FIG. 1 summarizes XRD spectra of the hydroxylated boron alkene material prepared in example 1 of the present application and the preparation raw material magnesium diboride. As can be understood from FIG. 1, magnesium diboride treated by the method of example 1 is derived from MgB 2 The multiple peak of (a) evolved into a single peak of borolene, indicating MgB 2 The etching of the interlayer metal elements is finished, and the reaction is relatively complete.
FIG. 2 is a drawing of an embodiment of the present applicationThe infrared spectrum of the hydroboracene material obtained in example 1. Wherein, 1616cm -1 Peaks at (B) correspond to B-H-B bonds, 638cm -1 The peak at (a) corresponds to B-OH, namely the hydroxylated borane, and the XRD pattern of fig. 1 can indicate that the successful etching of the present application results in a borane material indicating hydroxylation.
Fig. 3 and 4 are the FSEM photograph and AFM characterization results of the hydroboracene material obtained in example 1 of the present application, respectively. From the pictures, it can be known that the hydroboracene material prepared by the method has a sheet structure and good dispersibility, and no aggregate is formed, so that the feasibility of the preparation method is verified. Further, as can be understood from FIG. 4, the thickness of the resulting hydroboracene material was 3.64nm.
The hydroboracene material obtained in example 1 was dispersed in deionized water to obtain a hydroboracene dispersion. FIG. 5 is a photograph showing the Tyndall effect of the hydroboralene dispersion. As can be seen from fig. 5, the hydroboracene has a good dispersibility in water and can form a transparent colloid.
Example 2
Mixing 100mg of magnesium diboride with 2mL of deionized water at room temperature, and carrying out ultrasonic treatment for 5 minutes at the power of 550W to obtain a magnesium diboride dispersion liquid; meanwhile, 5mL of magnesium chloride solution with the concentration of 2mol/L is prepared and stirred for 10 minutes at the rotating speed of 800 r/min; the magnesium diboride dispersion is added into a magnesium chloride solution drop by drop (added in multiple times, the addition is finished in about 2 minutes), the stirring is continued at room temperature after the addition is finished, and when the color of the system solution is observed to be changed from black to brown, the stirring is stopped (the total stirring time is about 24 hours), so as to obtain a reaction material. Then washing the reaction materials for 3 times by using 5mL of hydrochloric acid with the concentration of 1mol/L, and then washing the reaction materials for multiple times by using deionized water until the pH value of a water washing solution is neutral; and finally, drying for 20 hours by using a freeze dryer to obtain the hydroxyl boron alkene material.
Example 3
A boroxine material whose preparation method of example 2 differs in that: the concentration of the magnesium chloride solution was 5mol/L.
Example 4
A boroxine material whose preparation method of example 2 differs 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 carrying out ultrasonic treatment for 5 minutes at the power of 600W to obtain a magnesium diboride dispersion liquid; meanwhile, 5mL of ferric chloride solution with the concentration of 5mol/L is prepared and stirred for 10 minutes at the rotating speed of 500 r/min; and (3) dropwise adding the magnesium diboride dispersion into the ferric chloride solution (adding the magnesium diboride dispersion in multiple times, wherein the adding is completed within about 2 minutes), continuously stirring at room temperature after the dropwise adding is completed, and stopping stirring when the color of the system solution is observed to be changed from black to brown (the total stirring time is about 24 hours) to obtain a reaction material. Then washing the reaction materials for 3 times by using 5mL of hydrochloric acid with the concentration of 1mol/L, and then washing the reaction materials for multiple times by using deionized water until the pH value of a water washing solution is neutral; and finally, drying for 20 hours by using a freeze dryer to obtain the hydroxyl boron alkene material.
Example 6
A boroxine material whose preparation method of example 5 differs in that: the concentration of the ferric chloride solution was 3.5mol/L.
Example 7
A boroxine material whose preparation method of example 5 differs in that: the concentration of the ferric chloride solution was 2mol/L.
FIG. 6 summarizes the XRD patterns of the borolene hydroxylate materials prepared in examples 2-4. FIG. 7 summarizes the XRD patterns of the boroxine materials prepared in examples 5-7. As can be seen from FIGS. 6-7, the magnesium chloride solutions of different concentrations and the ferric chloride solutions of different concentrations can be used to extract MgB from MgB as in example 1 2 The multiple peak of (2) evolved to a single peak of borolene, indicating MgB 2 The etching of the interlayer metal elements is finished, and the reaction is relatively complete.
Example 8
Mixing 120mg of aluminum diboride with 2mL of deionized water at room temperature, and carrying out ultrasonic treatment for 5 minutes at the power of 550W to obtain an aluminum diboride dispersion liquid; meanwhile, 5mL of ferric chloride solution with the concentration of 4mol/L is prepared and stirred for 10 minutes at the rotating speed of 500 r/min; and (3) dropwise adding the aluminum diboride dispersion into the ferric chloride solution (adding in multiple times, wherein the adding is finished within about 2 minutes), continuously stirring at room temperature after the dropwise adding is finished, and stopping stirring when the color of the system solution is observed to be changed from black to brown (the total stirring time is about 19 hours) to obtain a reaction material. Then washing the reaction materials for 3 times by using 5mL of hydrochloric acid with the concentration of 1mol/L, and then washing the reaction materials for multiple times by using deionized water until the pH value of a water washing solution is neutral; and finally, drying for 20 hours by using a freeze dryer to obtain the hydroxyl boron alkene material.
FIG. 8 is an AFM image of a boroxine material produced by example 8 and a layer thickness height map thereof. As can be seen from fig. 8, the hydroboracene material has a plate shape with a thickness of about 4.3nm.
Application examples
The boron hydride alkene hydroxylation material prepared by the embodiment of the application is used for modifying the zinc battery diaphragm. Illustratively, the preparation of the modified membrane comprises the following steps:
1) Adding the hydroxylated borane material prepared in the example 1 into an NMP solvent, and ultrasonically dispersing for 40 minutes at the power of 500W to obtain borane dispersion liquid with the concentration of 1 mg/mL; soaking the glass fiber diaphragm in an NMP solvent for 10-20 minutes;
2) And then carrying out vacuum filtration on the 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 carrying out vacuum drying for 16 hours at 65 ℃ to obtain the 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 hydroxidized boron olefin material, a modification layer with a deep gray level is formed on the surface of the glass fiber diaphragm. In the obtained modified diaphragm, the load capacity of the hydroxyl boron alkene material is 1mg/cm 2 The thickness of the modification layer is about 11.1 μm.
Preparation of a zinc ion battery, comprising the steps of: two zinc sheets are respectively used as a positive electrode and a negative electrode and are stacked with the modified diaphragm, and the modified diaphragm is arranged between the two zinc sheets to obtain a battery cell; the battery core is accommodated in a battery shell, an electrolyte (specifically, 120 mu L of zinc sulfate solution with the concentration of 2 mol/L) is injected, and then the battery shell is sealed, so that the CR2032 type symmetrical button battery is obtained. The symmetrical cell is designated as S1.
In order to highlight the beneficial effects of the application, the CR2032 type symmetrical button battery is assembled by adopting an unmodified glass fiber diaphragm and a zinc sheet and is marked as D1. After the assembly of each cell, the cells were allowed to stand for 6-8 hours before electrochemical performance testing.
Placing the symmetric batteries S1 and D1 at 5mA cm -2 Current density of 1mAh · cm -2 Electrochemical deposition/stripping cycle performance testing was performed at face volume of (a). Fig. 10 is a graph comparing the obtained time-voltage curves. As can be understood from fig. 10, the cycle life of the symmetric cell D1 does not exceed 450h, while the cycle life of the symmetric cell S1 can exceed 2000h, and the polarization voltage is only 66mV, and compared to the S1 cell, the polarization voltage is as high as 100mV in less than 400h, and a short circuit has occurred, and the cycle stability of the zinc symmetric cell S1 is significantly improved. This demonstrates that the separator modified with hydroboracene is beneficial for achieving uniform deposition of zinc, thereby achieving the effects of suppressing zinc dendrites, preventing the zinc dendrites from piercing the separator, and prolonging the cycle life of the battery. After that, the cell was disassembled and FSEM characterization was performed on the separated zinc negative electrode, and the results are shown in fig. 11. As can be seen from fig. 11, after the cycle test, the cathode surface of the battery assembled with the unmodified separator found many dendritic zinc dendrites, while after the cycle test, the cathode surface of the battery assembled with the modified separator showed a smooth and dense deposition layer, which indicates that the modified separator effectively inhibits the growth of zinc dendrites on the cathode surface.
In addition, the hydroboracene materials obtained in examples 2 to 8 were used for preparing modified separators and assembled into symmetrical zinc batteries, and the obtained symmetrical batteries were respectively designated as S2, S3, S4, S5, S6, S7 and S8. Wherein, at 5mA cm -2 Current density of 1mAh · cm -2 The electrochemical deposition/stripping cycle performance test is carried out under the surface capacity of (1), the cycle life of the batteries S2-S7 can exceed 1000h, and the cycle life of the battery S8 exceeds 800h, which are much longer than that of the D1 battery.
The above-described embodiments are merely illustrative of several exemplary embodiments of the present application, which are described in more detail and detail, but are not to be construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, and these variations and modifications belong to the protection scope of the present application.

Claims (16)

1. A preparation method of a hydroboracene material is characterized by comprising the following steps:
(1) Adding the layered metal boride into water, and performing ultrasonic dispersion to obtain a boron source dispersion liquid;
preparing a metal chloride aqueous solution, wherein the metal chloride aqueous solution comprises a zinc chloride aqueous solution with the concentration of 8-10mol/L, or a magnesium chloride aqueous solution with the concentration of 2-5mol/L, or a ferric chloride aqueous solution with the concentration of 2-5 mol/L;
(2) At room temperature, dropwise adding the boron source dispersion liquid into the metal chloride aqueous solution, and continuously stirring until the system color does not change any more, so as to obtain a reaction material;
(3) And centrifuging the obtained reaction material, collecting a solid, and sequentially washing the solid with hydrochloric acid and water for multiple times to obtain the solid material, namely the boron-ene hydroxylation material.
2. The method of 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 the ultrasonic dispersion in step (1) is performed at a power of 400 to 700W.
4. The production method according to claim 1, wherein in the step (2), the molar ratio of the mass of the layered metal boride to the magnesium chloride or the iron chloride in the boron source dispersion liquid is 20: (2-5) g/mol; the molar ratio of the mass of the layered metal boride in the boron source dispersion liquid to the zinc chloride is 20: (8-10) g/mol.
5. The modified diaphragm for the zinc battery is characterized by comprising a diaphragm base material, wherein a modification layer is arranged on one side, facing the negative electrode of the zinc battery, of the diaphragm base material, and the modification layer comprises a boron-ene-hydroxide material.
6. The modified membrane of claim 5, wherein the modified membrane has a boron hydride ene material loading of 0.5 to 1.5mg/cm 2 。
7. The modified membrane of claim 5, wherein the thickness of the modification layer is from 5 μm to 15 μm.
8. The modified membrane of claim 5 wherein the boratene material is bonded to the membrane substrate by vacuum filtration.
9. The modified membrane according to any one of claims 5 to 8, wherein the hydroxaldehyde material is obtained by the production method according to any one of claims 1 to 4.
10. A preparation method of a modified diaphragm for a zinc battery is characterized by comprising the following steps:
(1) Preparing a dispersion liquid containing a modification layer material and a first solvent, wherein the modification layer material comprises a boron-ene-hydroxide material;
(2) And carrying out vacuum filtration on the dispersion liquid on the diaphragm substrate so as to enable the boron-alkene-hydroxide material to be distributed on the surface of the diaphragm substrate to form a modification layer, and then carrying out vacuum drying to obtain the modified diaphragm with the modification layer on the surface.
11. The production method according to claim 10, wherein the dispersion liquid has a mass-to-volume concentration ratio of the modification layer material to the first solvent of (0.5 to 1.0): 1mg/mL.
12. The production method according to claim 10 or 11, characterized in that the separator substrate is further soaked with a first solvent before the dispersion is vacuum-filtered to the separator substrate.
13. A zinc ion battery comprising the modified separator as defined in any one of claims 5 to 9.
14. The zinc-ion battery of claim 13, further comprising a positive electrode, a negative electrode, and an electrolyte, wherein the modified separator is disposed between the positive electrode and the negative electrode, and the modification layer is adjacent to the negative electrode.
15. The application of the hydroxyl boron alkene material in a zinc ion battery.
16. The use of claim 15, wherein the hydroxalated borolene material is disposed on a surface of a separator of the zinc ion battery, and/or on a surface of a negative electrode of the zinc ion battery.
CN202211078930.XA 2022-09-05 2022-09-05 Preparation method and application of hydroxylated boron alkene material Active CN115385350B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211078930.XA CN115385350B (en) 2022-09-05 2022-09-05 Preparation method and application of hydroxylated boron alkene material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211078930.XA CN115385350B (en) 2022-09-05 2022-09-05 Preparation method and application of hydroxylated boron alkene material

Publications (2)

Publication Number Publication Date
CN115385350A true CN115385350A (en) 2022-11-25
CN115385350B CN115385350B (en) 2023-08-18

Family

ID=84123872

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211078930.XA Active CN115385350B (en) 2022-09-05 2022-09-05 Preparation method and application of hydroxylated boron alkene material

Country Status (1)

Country Link
CN (1) CN115385350B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107055561A (en) * 2017-05-05 2017-08-18 燕山大学 A kind of preparation method of boron alkene
CN107487776A (en) * 2016-06-13 2017-12-19 北京化工大学 A kind of method that liquid phase method prepares stratiform boron material
CN109336127A (en) * 2018-11-30 2019-02-15 深圳大学 A kind of boron alkene and preparation method thereof
CN111072041A (en) * 2019-12-24 2020-04-28 燕山大学 Method for rapidly preparing two-dimensional boron alkene
DE102019111225A1 (en) * 2019-04-30 2020-11-05 Forschungsverbund Berlin E.V. Process for producing a 2D material, 2D material and its applications
CN112928387A (en) * 2021-01-28 2021-06-08 厦门大学 Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm
CN113023742A (en) * 2021-05-10 2021-06-25 陕西师范大学 Method for preparing high-crystallinity and uniform-thickness boron alkene by hydrochloric acid assisted liquid phase oxidation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107487776A (en) * 2016-06-13 2017-12-19 北京化工大学 A kind of method that liquid phase method prepares stratiform boron material
CN107055561A (en) * 2017-05-05 2017-08-18 燕山大学 A kind of preparation method of boron alkene
CN109336127A (en) * 2018-11-30 2019-02-15 深圳大学 A kind of boron alkene and preparation method thereof
DE102019111225A1 (en) * 2019-04-30 2020-11-05 Forschungsverbund Berlin E.V. Process for producing a 2D material, 2D material and its applications
CN111072041A (en) * 2019-12-24 2020-04-28 燕山大学 Method for rapidly preparing two-dimensional boron alkene
CN112928387A (en) * 2021-01-28 2021-06-08 厦门大学 Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm
CN113023742A (en) * 2021-05-10 2021-06-25 陕西师范大学 Method for preparing high-crystallinity and uniform-thickness boron alkene by hydrochloric acid assisted liquid phase oxidation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHAO HAN等: ""2D boron nanosheet architectonics: opening new territories by smart functionalization"", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Also Published As

Publication number Publication date
CN115385350B (en) 2023-08-18

Similar Documents

Publication Publication Date Title
Zhang et al. Ultrathin and super-tough membrane for anti-dendrite separator in aqueous zinc-ion batteries
CN112117435B (en) All-solid-state lithium battery positive plate, preparation method thereof and all-solid-state lithium battery
CN111916716A (en) PVDF-TiO2Preparation method of composite membrane and application of composite membrane in inhibiting growth of lithium dendrite
CN112670450A (en) Negative pole piece for solid-state battery and preparation method and application thereof
Chen et al. “Sticky” carbon coating enables high-area-capacity lithium storage of silicon-graphitic carbon hybrid
CN114284475B (en) Preparation method of three-dimensional structured composite lithium metal anode and product thereof
CN111883763A (en) Nitrogen-doped carbon nano SnO2Composite material and preparation method and application thereof
CN107482184A (en) A kind of preparation method of lithium titanate cathode of lithium ion battery composite
CN112751008B (en) Polyphenol modified zinc-iron based heterojunction oxide carbon nano lithium ion battery cathode composite material and preparation method thereof
Deng et al. In-situ MOFs coating on 3D-channeled separator with superior electrolyte uptake capacity for ultrahigh cycle stability and dendrite-inhibited lithium-ion batteries
CN109802078A (en) A kind of soft graphite alkenyl composite polyimide material of membrane structure, preparation method and applications
CN116344781B (en) Method for coating halide electrolyte on surface of electrode active material and active material
CN112186153A (en) Lithium cathode with interface nanosheet protective layer and preparation method thereof
CN109860557B (en) Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery
CN115385350B (en) Preparation method and application of hydroxylated boron alkene material
CN114843700B (en) Highly ordered end-group MXene and preparation method and application thereof
CN115939497A (en) Ultrathin elastic solid electrolyte membrane and preparation method thereof
CN115663157A (en) Hard carbon composite material for lithium ion battery and preparation method thereof
CN111799506B (en) Composite gel polymer electrolyte applying polymer nano-filler, preparation method and solid-state lithium battery using electrolyte
CN114551782A (en) Lithium metal negative electrode coated with protective layer and preparation method and application thereof
CN113571764A (en) Composite solid electrolyte membrane and preparation method thereof
CN111129437A (en) Method for passivating surface of lithium cathode
CN113620295B (en) MXene-CoTe composite diaphragm material and preparation method and application thereof
Hu et al. Solid-state polymeric coating as regulating deposition layer for dendrite-free and stable rechargeable aqueous Zn metal anode
CN115207561B (en) Polyolefin composite film and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant