CN116063875A

CN116063875A - Application of organic column support montmorillonite in preparation of zinc ion battery negative electrode protection material

Info

Publication number: CN116063875A
Application number: CN202310059317.1A
Authority: CN
Inventors: 胡超权; 廖丹; 王勇
Original assignee: Zhongke Nanjing Green Manufacturing Industry Innovation Research Institute
Current assignee: Zhongke Nanjing Green Manufacturing Industry Innovation Research Institute
Priority date: 2023-01-16
Filing date: 2023-01-16
Publication date: 2023-05-05

Abstract

The invention provides an application of organic pillared montmorillonite in preparing a zinc ion battery negative electrode protection material, wherein the organic pillared montmorillonite is obtained by pillaring montmorillonite by any one or a combination of at least two of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide. By inserting organic cations between the layered structures of montmorillonite, the interlayer spacing of montmorillonite is enlarged, providing a wider path for zinc ion transport. The organic pillared montmorillonite is used as a protective material to be coated on the negative electrode to form a protective layer, the existence of the protective layer isolates the direct contact between the zinc negative electrode and the acid electrolyte, the corrosion of the negative electrode is weakened, the growth of zinc dendrites is inhibited, and the electrochemical performance of the zinc ion battery is improved.

Description

Application of organic column support montmorillonite in preparation of zinc ion battery negative electrode protection material

Technical Field

The invention belongs to the technical field of zinc ion batteries, and relates to application of organic pillared montmorillonite in preparation of a zinc ion battery negative electrode protection material.

Background

Among the various electrochemical systems, lithium ion batteries are leading in terms of energy density, service life, and storage stability. However, safety issues, high cost and limited lithium resources have hampered continued widespread use and subsequent development of lithium ion batteries. Zinc ion batteries are considered ideal alternatives to lithium ion batteries in particular fields due to their great advantages in terms of safety, cost, and acceptable energy density.

The problems of corrosion of the zinc cathode and dissolution of the positive electrode of the water-based zinc ion battery are unavoidable, and in addition, the growth of zinc dendrites is a great challenge which plagues the further development of the zinc ion battery. In the light of lithium metal battery research, many studies have demonstrated the benefits of surface and interface modification to inhibit dendrite growth and side reactions, which can generally be achieved through the use of a support or surface protective layer with careful design. In general, the electrode protection material should have characteristics of high specific surface area, excellent electron conductivity, stable structure, and abundant zinc deposition functional sites. And can inhibit dendrite growth and side reactions, but allow Zn ²⁺ Diffusion and deposition of ions. Some examples include ultra-thin TiO using atomic layer deposition ₂ Coating, nano porous CaCO ₃ Drop casting and Al of (2) ₂ O ₃ Is deposited. Although these materials can prevent dendrite growth and corrosion of zinc anode, diffusion of zinc ions through these coating materials is severely limited and affects battery performance, and these materials are generally expensive, and the preparation process is complicated, which is not advantageous for industrialization.

Natural clay is abundant throughout the world, and because of its abundant reserves, it is convenient to mine, and the average price of clay minerals is relatively low. Inorganic natural clays are generally composed of aluminum and magnesium silicates. At the chemical level, silicate layers are generally composed of alternating Si-O tetrahedra and Al-O octahedra. Silicate layers are classified into types 1:1 and 2:1.

Montmorillonite is the most widely studied clay material, which meets the characteristics of most layered clay materials, and the exchangeable cations at the interface and edges of the layers and sheets provide the possibility for ion exchange. The flakes are formed of one layer of Al-O octahedra sandwiched between two layers of Si-O tetrahedra. The interlayer serves as a high-speed channel for transporting exchangeable cations, zn ²⁺ Migrate into the interstices of the sheet under the drive of the electric field. However, conventional clay materials, while having channels that facilitate ion transport, are disadvantageous to zinc ion cell performance due to the small interlayer spacing that is detrimental to the rapid transport of zinc ions.

Therefore, how to set up the protective layer to the aqueous zinc ion battery, solve the problem that zinc negative pole corrodes and anodal dissolves, inhibit dendrite growth and side reaction, realize the fast transmission of zinc ion simultaneously, keep the excellent battery performance of zinc ion, have become the urgent problem of the field to be solved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an application of organic pillared montmorillonite in preparing a zinc ion battery negative electrode protection material.

In order to achieve the aim of the invention, the invention adopts the following technical scheme:

in a first aspect, the invention provides an application of organic pillared montmorillonite in preparing a zinc ion battery negative electrode protection material, wherein the organic pillared montmorillonite is prepared by pillaring montmorillonite with any one or a combination of at least two of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.

Preferably, the organic pillared montmorillonite is decaalkyl trimethyl ammonium bromide pillared montmorillonite.

Preferably, the preparation method of the organic pillared montmorillonite comprises the following steps: mixing the propping agent, montmorillonite and water, reacting, centrifugally collecting precipitate, and drying to obtain the final product;

the pillared agent is selected from any one or a combination of at least two of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.

Preferably, the temperature of the reaction is 60-80 ℃, e.g., 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, etc., and the time of the reaction is 2-4 hours, e.g., 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.2 hours, 3.5 hours, 3.8 hours, 4 hours, etc.

Preferably, the mass ratio of the pillared agent to the montmorillonite is (0.5-1.0): 2.0-4.0.

Specific values in the above (0.5 to 1.0) are, for example, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, etc.

Specific values in the above (2.0 to 4.0) are, for example, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, etc.

The mass ratio of the pillared to montmorillonite is further preferably 0.3 to 0.4, for example 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, etc.

Preferably, the mixing mode comprises: the aqueous solution of the propping agent is added dropwise to the aqueous montmorillonite suspension.

Preferably, the concentration of the propping agent in the aqueous solution of the propping agent is 1.5-1.0g/50mL.

Preferably, the concentration of montmorillonite in the aqueous montmorillonite suspension is 2.0-4.0g/100mL.

Preferably, the montmorillonite water suspension is obtained by mixing montmorillonite and water and stirring for 0.5-2 h:

preferably, the speed of centrifugation is 4000-6000 rpm, such as 4000 rpm, 4200 rpm, 4500 rpm, 4800 rpm, 5000 rpm, 5200 rpm, 5500 rpm, 5800 rpm, 6000 rpm, etc.

Preferably, the mixing of the pillared agent and the montmorillonite with water further comprises washing the montmorillonite with water and drying.

Preferably, the washing mode comprises mixing montmorillonite with water, stirring, centrifuging and collecting precipitate.

Preferably, the centrifugation in the washing specifically comprises: centrifuging at 2000-4000 rpm, collecting precipitate, centrifuging the suspension at 8000-10000 rpm, and collecting precipitate.

Specific values among the above 2000 to 4000 rpm are, for example, 2000 rpm, 2200 rpm, 2500 rpm, 2800 rpm, 3000 rpm, 3200 rpm, 3500 rpm, 3800 rpm, 4000 rpm, etc.

Specific values among the above 8000-10000 rpm are, for example, 8000 rpm, 8200 rpm, 8500 rpm, 8800 rpm, 9000 rpm, 9200 rpm, 9500 rpm, 9800 rpm, 10000 rpm, etc.

In a second aspect, the present invention provides an aqueous zinc ion battery comprising a zinc anode, an organic pillared montmorillonite, a binder, a cathode and a separator;

the organic pillared montmorillonite is prepared by pillaring montmorillonite with any one or a combination of at least two of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.

Preferably, the preparation method of the organic pillared montmorillonite is as described in the first aspect, and is not described herein.

Experiments show that in the preparation method of the organic pillared montmorillonite, the reaction temperature, the reaction time and the related centrifugal rotating speed have little influence on the performance of the prepared water-based zinc ion battery, so that the technical personnel in the field can design the parameters by themselves, and the effects of the invention can be realized theoretically.

In a third aspect, the present invention provides a method for preparing an aqueous zinc-ion battery according to the second aspect, the method comprising: mixing organic pillared montmorillonite, a binder and a solvent to form slurry, coating the slurry on a zinc cathode, drying, and assembling with a positive electrode and a diaphragm to obtain the composite material.

Preferably, the weight ratio of the organic pillared montmorillonite to the binder is (8-10): 1.

Specific values in the above (8-10) are, for example, 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, 10, etc.

When the ratio of the binder (PVDF and the like) to the organic pillared montmorillonite is low, the adhesiveness of the negative electrode protective layer of the aqueous zinc ion battery is poor, and the protective layer is easy to fall off from the surface of the negative electrode, because the content of the pillared montmorillonite is too high and the content of the binder is too low, the formed protective layer coating material is easy to fall off, the protective force on the negative electrode is insufficient, the growth of zinc negative electrode dendrites cannot be effectively inhibited, the reversible capacity of the aqueous zinc ion battery is reduced, and the capacity retention rate is reduced. When the ratio of the binder to the organic pillared montmorillonite is higher, the content of the binder is too much, so that the internal resistance of the battery is increased, and meanwhile, the content of the pillared montmorillonite is reduced, so that the specific capacity and the capacity retention rate of the water-based zinc ion battery are reduced. Therefore, the above ratio is preferably selected for optimum effect.

Preferably, the mixing is performed at 15-40 ℃, e.g., 15 ℃, 17 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 37 ℃, 40 ℃, etc., and the mixing is performed for a period of 12-24 hours, e.g., 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.

Preferably, the mixing is performed under magnetic stirring or mechanical stirring.

Preferably, the drying temperature is 60-80 ℃, for example 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, etc.

Preferably, the binder comprises polyvinylidene fluoride (PVDF).

Preferably, the solvent comprises N-methylpyrrolidone.

Preferably, the zinc anode comprises zinc foil.

Preferably, the positive electrode includes a manganese oxide electrode.

Preferably, the separator comprises a glass fiber film.

Preferably, the means of coating includes, but is not limited to, coating with an applicator.

The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.

Compared with the prior art, the invention has the following beneficial effects:

the invention selects natural montmorillonite minerals as raw materials, and takes metal ions (Na) capable of ion exchange into account among montmorillonite layers ⁺ ，Al ³⁺ Etc.), it is proposed to prop montmorillonite original soil with organic cations such as dodecyl trimethyl ammonium bromide, and the prop montmorillonite has an extended and steady nanoscale interlayer tunnel, which is favorable for rapid transmission of zinc ions, ensures excellent cycling stability of the zinc ion battery during deep cycling, and can be used as a zinc ion battery electrode protection material to be coated on a zinc cathode, thereby greatly improving the performance of the zinc ion battery.

In the zinc ion battery electrode protection material, organic cations such as dodecyl trimethyl ammonium bromide are inserted between the layered structures of the montmorillonite, so that expansion of interlayer spacing is realized, a wider channel is provided for zinc ion transmission, and rapid transmission of zinc ions in the water-based zinc ion battery electrode protection material is facilitated; the organic cations inserted into the montmorillonite provide strong support for the layered structure of the montmorillonite, so that the structural stability of the electrode protection material of the aqueous zinc ion battery is improved, and the deep circulation of the aqueous zinc ion battery is satisfied; the aqueous zinc ion battery assembled by the electrode protection material has excellent reversible capacity and cycle stability.

In the preparation method of the organic pillared montmorillonite, the used raw materials have wide sources, low cost and easy obtainment; simple process, low requirement on experimental conditions, low production cost and meeting the requirement of industrialization.

According to the invention, the electrode protection material is coated on the surface of the zinc anode to obtain the anode with the protection layer, so that the acidic aqueous electrolyte is prevented from directly contacting with the zinc anode, thereby inhibiting the corrosion of the zinc anode, inhibiting the growth of zinc dendrites, avoiding the problems of rapid capacity decay and the like of the aqueous zinc ion battery, and effectively improving the performance of the aqueous zinc ion battery.

Drawings

FIG. 1 is a graph showing the results of transmission electron microscopy characterization of the deca-alkyl trimethyl ammonium bromide pillared montmorillonite of example 1.

FIG. 2 is an X-ray diffraction pattern of decaalkyl trimethyl ammonium bromide pillared montmorillonite in example 1 and unipillared montmorillonite in comparative example 1.

Fig. 3 is a small angle (3-10 °) X-ray diffraction pattern of decaalkyl trimethyl ammonium bromide pillared montmorillonite in example 1 and non-pillared montmorillonite in comparative example 1.

FIG. 4 shows that the aqueous zinc ion button cell assembled from the decanyl trimethyl ammonium bromide pillared montmorillonite used as the electrode protection material in example 1 is 0.1Ag ^-1 Cyclic test patterns at current density of (c).

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

In the following examples, all reagents and consumables were purchased from the reagent manufacturers routine in the art unless specifically indicated; unless otherwise indicated, all methods and techniques used are those conventional in the art.

The montmorillonite original soil is off-white sodium-based montmorillonite produced by Zhejiang Feng Hong new material Co., ltd.

Example 1

The embodiment provides a preparation method of a dodecyl trimethyl ammonium bromide pillared montmorillonite-based electrode protection material, which comprises the following specific steps:

s1, stirring and dispersing montmorillonite raw soil with deionized water, and centrifuging at 3000 rpm for 10 minutes. After the first centrifugation, the upper suspension was again centrifuged at 9000 rpm for 3 minutes. The collected precipitate was dried under vacuum at 60 ℃, then ground and sieved (200 mesh) to obtain the washed montmorillonite raw soil.

S2, dissolving dodecyl trimethyl ammonium bromide (0.70 g) in deionized water (50 mL) to form a transparent solution.

S3, uniformly dispersing the montmorillonite raw soil (2.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 0.5 hour to obtain a uniform montmorillonite suspension.

S4, dripping the solution obtained in the step S2 into the suspension obtained in the step S3, and keeping the mixed solution stirred for 3 hours at 80 ℃. After the reaction, the mixture was collected at 5000 rpm for 5 minutes to collect the precipitate, which was then washed with deionized water. Finally, the collected organically modified montmorillonite is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Example 2

s1, stirring and dispersing montmorillonite raw soil with deionized water, and centrifuging at 3000 rpm for 10 minutes. After the first centrifugation, the upper suspension was again centrifuged at 9000 rpm for 3 minutes. The collected precipitate was dried under vacuum at 60 ℃ and then ground and sieved (200 mesh).

S3, uniformly dispersing the montmorillonite raw soil (3.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 2 hours to obtain a uniform montmorillonite suspension.

S4, dripping the solution obtained in the step S2 into the suspension obtained in the step S3, and keeping the mixed solution stirred for 4 hours at 70 ℃. After the reaction, the mixture was collected at 6000 rpm for 3 minutes to precipitate, and then washed with deionized water several times. Finally, the collected organically modified montmorillonite is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Example 3

S2, dissolving dodecyl trimethyl ammonium bromide (1.0 g) in deionized water (50 mL) to form a transparent solution.

S3, uniformly dispersing montmorillonite raw soil (4.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 1.0 hour to obtain uniform montmorillonite suspension.

S4, dripping the solution obtained in the step S2 into the suspension obtained in the step S3, and keeping the mixed solution stirred for 4 hours at the temperature of 60 ℃. After the reaction, the mixture was collected at 4000 rpm for 8 minutes to collect the precipitate, which was then washed with deionized water multiple times. Finally, the collected organically modified montmorillonite is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Example 4

s1, stirring and dispersing montmorillonite raw soil with deionized water, and centrifuging at 3000 rpm for 10 minutes. After the first centrifugation, the upper suspension was again centrifuged at 9000 rpm for 3 minutes. The collected precipitate was dried in vacuo, then ground and sieved (200 mesh).

S2, dissolving dodecyl trimethyl ammonium bromide (0.50 g) in deionized water (50 mL) to form a transparent solution.

S3, uniformly dispersing the montmorillonite raw soil (2.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 1.0 hour to obtain a uniform montmorillonite suspension.

S4, dripping the solution obtained in the step S2 into the suspension obtained in the step S3, and keeping the mixed solution stirred for 2 hours at 80 ℃. After the reaction, the mixture was collected at 5000 rpm for 5 minutes to collect the precipitate, which was then washed with deionized water multiple times. Finally, the collected organically modified montmorillonite is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Example 5

S3, uniformly dispersing the montmorillonite raw soil (2.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 2h to obtain a uniform montmorillonite suspension.

S4, dripping the solution obtained in the step S2 into the suspension obtained in the step S3, and keeping the mixed solution stirred for 3 hours at 80 ℃. After the reaction, the mixture was collected at 5000 rpm for 5 minutes to collect the precipitate, which was then washed with deionized water multiple times. Finally, the collected organically modified montmorillonite is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Example 6

s1, stirring and dispersing montmorillonite raw soil with deionized water, and centrifuging at 3000 rpm for 10 minutes. After the first centrifugation, the upper suspension was again centrifuged at 9000 rpm for 3 minutes. The collected precipitate was dried in vacuo (60 ℃) and then ground and sieved (200 mesh).

S3, uniformly dispersing the montmorillonite raw soil (3.0 g) obtained by washing in the step S1 in 100mL of deionized water, and then stirring for 0.5 hour to obtain a uniform montmorillonite suspension.

Example 7

This example provides a method for preparing a tetradecyltrimethylammonium bromide pillared montmorillonite-based electrode protective material, which differs from example 1 only in that the procedure is to replace the dodecyl trimethyl ammonium bromide (molecular weight 280.29) with an equimolar amount of tetradecyltrimethylammonium bromide (molecular weight 336.4, weight 0.84 g), otherwise refer to example 1.

Example 8

This example provides a method for preparing octadecyl trimethyl ammonium bromide pillared montmorillonite-based electrode protection material, which differs from example 1 only in that dodecyl trimethyl ammonium bromide is replaced with equimolar amount of octadecyl trimethyl ammonium bromide (molecular weight 392.5, weight 0.98 g), otherwise refer to example 1.

Comparative example 1

This comparative example provides a method for preparing an undeployed montmorillonite-based electrode protective material, which is different from example 1 only in that no pillared reaction with dodecyl trimethyl ammonium bromide is carried out, and other reference example 1 comprises the following specific steps:

the montmorillonite raw soil washed in the step S1 of the example 1 is dried in vacuum at 60 ℃, and then ground, sieved and collected for standby.

Characterization of pillared montmorillonite

(1) Transmission electron microscopy was performed on the decaalkyl trimethylammonium bromide pillared montmorillonite prepared in example 1, and the obtained TEM image is shown in FIG. 1.

(2) X-ray diffraction is carried out on the non-pillared montmorillonite and the decaalkyl trimethyl ammonium bromide pillared montmorillonite in the comparative example 1, and the obtained X-ray diffraction patterns are shown in fig. 2 and 3; in this, the small angle XRD diffractogram clearly shows (fig. 3) that the montmorillonite (001) plane peak pillared with decaalkyl trimethyl ammonium bromide is slightly shifted to a lower angle (5.00 °) than the montmorillonite original earth (7.09 °). According to bragg equation 2dsin θ=nλ, the interlayer spacing of montmorillonite was widened from 1.25nm to 1.76nm. It is proved that long-chain dodecyl trimethyl ammonium bromide cation can enter interlayer of montmorillonite and play a role in widening interlayer spacing.

Zinc ion battery long-cycle test

An aqueous zinc ion battery was prepared using the electrode protection materials of examples 1 to 8 and comparative example 1, as follows:

polyvinylidene fluoride (PVDF), an electrode protection material are weighed, mixed into slurry (the mass ratio of PVDF to the electrode protection material is 1:9) in a solvent N-methyl pyrrolidone (NMP) at room temperature, the slurry is coated on zinc foil by using a coater, dried in a vacuum drying oven at 60-80 ℃, and then cut into discs with the diameter of 14mm, so as to obtain the negative electrode. And (3) taking the glass fiber membrane as a diaphragm, taking the manganese oxide electrode as an anode, and assembling the anode, the cathode and the diaphragm to obtain the water-based zinc ion button cell.

The water-based zinc ion button cell is set at 0.1Ag ^-1 The cycle performance test was performed at a current density of (1) and the number of cycles was 100, and the discharge capacity (reversible capacity) and capacity retention data after 100 cycles were obtained are shown in table 1, and an example is shown in fig. 4 (example 1).

TABLE 1

The results show that: when the non-pillared montmorillonite is used as an electrode protection material, the reversible capacity of the obtained zinc ion battery after 100 times of circulation is 148.2mAh g ^-1 The capacity retention rate is 65.8%, and the reversible capacity of the zinc ion battery obtained by using the organic pillared montmorillonite after 100 times of circulation is improved to 161mAh g ^-1 The capacity retention rate is improved to above 71%, and the battery performance is remarkably improved. And after multiple cycles, the coulombic efficiency after stabilization can still approach 100%, which shows that the organic pillared montmorillonite can lead the zinc ion battery to have better cycle stability and reversibility as an electrode protection material.

The zinc ion battery obtained by using the dodecyl trimethyl ammonium bromide pillared montmorillonite has the best performance compared with other cations, and the possibility is that after the dodecyl trimethyl ammonium bromide pillared montmorillonite is used, the spacing of montmorillonite sheets and the size of zinc ions hydrate are optimally adapted, so that the zinc ions can pass through, and the performance of the battery can be exerted. The spacing between the post-support back sheet layers is too small, which is not beneficial to the rapid and smooth passing of zinc ions, thereby affecting the battery performance; notably, the use of larger organic cations (tetradecyltrimethylammonium bromide or octadecyltrimethylammonium bromide) to support montmorillonite did not further enhance performance.

In summary, in the organic pillared montmorillonite, organic cations such as dodecyl trimethyl ammonium bromide are inserted between the layered structures of the montmorillonite, so that the spacing between montmorillonite layers is increased, the rapid and smooth passing of zinc ions is facilitated, and the battery performance is improved; the cations inserted into the montmorillonite provide strong support for the layered structure of the montmorillonite, so that the structural stability of the electrode protection material of the aqueous zinc ion battery is improved, and the deep circulation of the aqueous zinc ion battery is satisfied; the aqueous zinc ion battery assembled by the electrode protection material of the aqueous zinc ion battery has excellent reversible capacity and cycle stability.

The raw materials used in the preparation method of the organic pillared montmorillonite are wide in sources, low in cost and easy to obtain; simple process, low requirement on experimental conditions, low production cost and meeting the requirement of industrialization.

According to the invention, the electrode protection material is coated on the surface of the zinc anode to obtain the anode with the protection layer, so that the acidic aqueous electrolyte is prevented from directly contacting with the zinc anode, the corrosion of the zinc anode is inhibited, the problems of rapid capacity decay and the like of the aqueous zinc ion battery are avoided, and the performance of the aqueous zinc ion battery is effectively improved.

The applicant states that the application of the organic pillared montmorillonite of the present invention in the preparation of a zinc-ion battery anode protection material is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.

In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

Claims

1. The application of the organic pillared montmorillonite in preparing the negative electrode protection material of the zinc ion battery is characterized in that the organic pillared montmorillonite is obtained by pillaring montmorillonite with any one or a combination of at least two of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.

2. The use according to claim 1, wherein the organic pillared montmorillonite is a decaalkyl trimethyl ammonium bromide pillared montmorillonite.

3. The use according to claim 1 or 2, wherein the preparation method of the organic pillared montmorillonite comprises the following steps: mixing the propping agent, montmorillonite and water, reacting, centrifugally collecting precipitate, and drying to obtain the final product;

4. The method according to claim 3, wherein the reaction is carried out at a temperature of 60-80 ℃ for a time of 2-4 hours.

5. The use according to claim 3 or 4, wherein the mass ratio of the pillared to montmorillonite is (0.5-1.0): 2.0-4.0.

6. The use according to any one of claims 3-5, wherein the mixing means comprises: dropwise adding the aqueous solution of the propping agent into the montmorillonite aqueous suspension;

preferably, the speed of centrifugation is 4000-6000 rpm;

7. The water-based zinc ion battery is characterized by comprising a zinc negative electrode, organic pillared montmorillonite, a binder, a positive electrode and a diaphragm;

8. The aqueous zinc-ion battery according to claim 7, wherein the organic pillared montmorillonite is a decaalkyl trimethyl ammonium bromide pillared montmorillonite.

9. A method of preparing the aqueous zinc-ion battery of claim 7 or 8, comprising: mixing organic pillared montmorillonite, a binder and a solvent to form slurry, coating the slurry on a zinc cathode, drying, and assembling with a positive electrode and a diaphragm to obtain the composite material.

10. The method for preparing the aqueous zinc ion battery according to claim 9, wherein the weight ratio of the organic pillared montmorillonite to the binder is (8-10) 1;

preferably, the mixing is carried out at 15-40 ℃ for a period of 12-24 hours.