An ultra-thin modified zinc material with a surface 3D pore structure and its preparation method and application

Abstract

The present invention discloses an ultra-thin modified zinc material with a surface 3D pore structure and its preparation method and application. The ratio of the (002) crystal plane to the (100) crystal plane on the surface of the zinc material is 1 (002) / I (100) ≥1; the pore size of the 3D pore structure on the surface of the zinc material is 0.5 to 5 μm. The zinc material is obtained by surface etching a zinc foil with an aminosulfonic acid solution. The directional control of the surface microstructure of the zinc foil can be achieved by simply adjusting the solution concentration and etching time. Based on the specific surface structure and crystal plane ratio of the zinc material, the aqueous zinc metal battery prepared using it as the battery negative electrode has excellent comprehensive performance. In particular, the high proportion of (002) crystal planes in the surface crystal planes of the zinc material can effectively inhibit the growth of zinc dendrites, thereby giving the zinc metal battery excellent cycle stability, discharge specific capacity and cycle life, which can meet the performance requirements of energy storage or power batteries.

Description

Technical Field

[0001] The present invention relates to an ultrathin modified zinc material, in particular to an ultrathin modified zinc material with a surface 3D pore structure and a preparation method and application thereof, belonging to the technical field of aqueous zinc metal batteries. Background Art

[0002] With the increasing popularity of new energy vehicles and the development of advanced energy storage technologies, aqueous batteries have attracted significant attention due to their low cost, non-toxicity, and safety. Aqueous zinc metal batteries (ZnM batteries) stand out due to their ease of operation, low potential, and high theoretical capacity. However, issues such as dendrite growth, corrosion, and side reactions not only challenge aqueous ZnM batteries with low Coulombic efficiency and short cycle life, but also further slow their commercialization.

[0003] Constructing artificial coatings, using electrolyte additives, modifying diaphragms, and constructing modified zinc anode substrates are effective strategies to alleviate the above problems. At present, the mainstream methods for constructing modified zinc anode substrates are: (1) depositing zinc on zinc-philic support materials such as carbon-based, alloys, and polymers; (2) using chemical reagents to etch the surface of metal zinc to form a 3D zinc anode. For the former, the introduction of additional substrates may lead to increased costs, larger volume, material deformation, and more difficult operation. Therefore, it is economical to directly etch metal zinc into a 3D structure. By optimizing the concentration and time of the etchant, the surface micromorphology of the zinc anode and the relative content of the (002) crystal plane can be adjusted, thereby effectively inhibiting the growth of zinc dendrites. In recent years, researchers have used acid etchants to modify metal zinc. For example, in literature 1 (Wen Q, Fu H, Wang Z, et al. A hydrophobic layer of amino acid enabling dendrite-free Zn anodes for aqueous zinc-ion batteries [J]. Journal of Materials Chemistry A, 2022, 10: 17501-17510.), L-cysteine ​​was used to etch metal zinc foil to obtain a Cys-Zn@Zn zinc negative electrode. However, the surface morphology of the Cys-Zn@Zn zinc negative electrode did not have obvious three-dimensional features, and the proportion of (002) crystal planes and electrochemically active sites could not be well improved. In addition, L-cysteine ​​is expensive, has low solubility, has an odor, and takes a long time to etch. In literature 2 (Cao P, Zhou X, Ran L, et al. The 3D nano-trench interface to manipulate the stripping / plating behavior for stable Zn anode [J]. Journal of Power Sources, 2022, 528: 231215.) Using concentrated hydrochloric acid to rapidly etch zinc foil and construct a three-dimensional groove interface, an E@Zn zinc anode was obtained. While the three-dimensional groove interface of this anode increased the electrochemically active sites on the electrode surface, it failed to effectively enhance the surface (002) crystal plane, resulting in minimal improvement in the battery's cycling performance. Furthermore, concentrated hydrochloric acid is volatile, highly corrosive, and highly harmful to the human body, and has high requirements for the operating environment. Furthermore, there are many different types of etchants, each with varying costs, volatility, toxicity, and the time required to process the zinc anode and the operating environment. Therefore, it is necessary to explore a metal zinc modification strategy that can preferentially expose the (002) crystal plane, is low-cost, non-volatile, non-toxic, and easy to operate.

[0004] The ultrathin modified zinc material with preferential crystal planes proposed in the present invention has a 3D hexagonal pore structure on its surface, which enriches the electrochemically active sites on the electrode surface and increases the relative content of the (002) crystal plane. In the battery, the ultrathin modified zinc material with preferential crystal planes effectively inhibits the growth of zinc dendrites and achieves a stable long cycle life. Summary of the Invention

[0005] In view of the problems existing in the prior art, the first object of the present invention is to provide an ultra-thin modified zinc material with a surface 3D pore structure. Based on the specific 3D pore structure on the surface of the material, the zinc material preferentially exposes the (002) crystal plane with lower surface energy, and improves the I (002) / I (100) Crystal face ratio. On the one hand, the specific microstructure can not only give the material rich electrochemical active sites and provide more nucleation sites for zinc ion deposition, but also the specific pore structure can adjust the surface crystal face ratio of the zinc material, prompting zinc ions to deposit in the horizontal direction, effectively inhibiting the growth of zinc dendrites in zinc batteries.

[0006] The second object of the present invention is to provide a method for preparing an ultra-thin modified zinc material with a surface 3D pore structure. This method uses an aminosulfonic acid solution to etch the surface of the zinc foil. Directional control of the surface microstructure of the zinc foil can be achieved by simply adjusting the solution concentration and etching time. This method has a simple process, low cost, and no harmful waste gas or waste liquid, making it suitable for large-scale industrial production.

[0007] The third object of the present invention is to provide an application of an ultra-thin modified zinc material with a surface 3D pore structure as a battery negative electrode to prepare an aqueous zinc metal battery. Based on the specific surface structure and crystal plane ratio of the modified zinc material of the present invention, the aqueous zinc metal battery prepared as the battery negative electrode has excellent comprehensive performance, especially by utilizing the high proportion of (002) crystal planes in the surface crystal planes of the zinc material, which can effectively inhibit the growth of zinc dendrites, thereby giving the zinc metal battery excellent cycle stability, discharge specific capacity and cycle life, which can meet the performance requirements of energy storage or power batteries.

[0008] In order to achieve the above technical objectives, the present invention provides an ultra-thin modified zinc material with a surface 3D pore structure, wherein the ratio of the (002) crystal plane to the (100) crystal plane on the surface of the zinc material is 1 (002) / I (100) ≥1; the pore size of the 3D pore structure on the surface of the zinc material is 0.5 to 5 μm.

[0009] As a preferred solution, the ratio of the (002) crystal plane to the (100) crystal plane on the surface of the zinc material is (002) / I (100) The range is 1 to 10.

[0010] As a preferred solution, the thickness of the zinc material is 5 to 30 μm. More preferably, the thickness of the new material is 20 μm.

[0011] As a preferred solution, the 3D pore structure on the surface of the zinc material is a multi-level hexagonal honeycomb structure with a pore diameter of 1 to 3 μm.

[0012] The present invention also provides a method for preparing an ultra-thin modified zinc material with a surface 3D pore structure. The metal zinc foil is cleaned and then immersed in an aminosulfonic acid solution for etching modification. After the modification is completed, it is cleaned and dried to obtain the material.

[0013] As a preferred solution, the purity of the metal zinc foil is ≥99%. More preferably, the purity of the metal zinc foil is 99.999%.

[0014] As a preferred solution, the solvent of the aminosulfonic acid solution is deionized water and / or liquid ammonia, and the concentration thereof is 0.1 to 1.5M.

[0015] As a preferred solution, the solvent of the sulfamic acid solution is deionized water, and its concentration is 1.0 to 1.5 M. More preferably, the concentration of the sulfamic acid solution is 1 M.

[0016] As a preferred solution, the time for the excessive volume impregnation is 10 to 60 minutes.

[0017] The present invention also provides an application of an ultra-thin modified zinc material with a surface 3D pore structure as a battery negative electrode to prepare an aqueous zinc metal battery.

[0018] As a preferred solution, the aqueous zinc metal battery includes a button cell and a soft pack cell.

[0019] As a preferred solution, the button battery consists of a positive electrode, a negative electrode, an electrolyte and a separator.

[0020] As a preferred solution, the soft-pack battery consists of a positive electrode, a negative electrode, an electrolyte, a separator, an aluminum tab and a nickel tab.

[0021] As a preferred solution, the positive electrode is composed of an active material, a conductive agent and a binder.

[0022] As a preferred solution, the active substance is at least one of a vanadium-based compound, a manganese-based compound, and a Prussian blue analogue. More preferably, the active substance is a vanadium-based compound.

[0023] As a preferred solution, the conductive agent is at least one of acetylene black, Ketjen black, carbon black, graphite, carbon nanotubes, and graphene. More preferably, the conductive agent is acetylene black.

[0024] As a preferred solution, the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene and carboxymethyl cellulose. More preferably, the binder is polyvinylidene fluoride.

[0025] As a preferred solution, the electrolyte is at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc chloride, zinc fluoride, zinc nitrate, zinc acetate and zinc perchlorate, and its concentration is 1 to 3 M. More preferably, the electrolyte is a 2 M zinc sulfate solution.

[0026] As a preferred solution, the diaphragm comprises at least one of filter paper, glass fiber and hydrophilic polyolefin membrane. Further preferably, the diaphragm is filter paper.

[0027] As a preferred solution, the separators are arranged in the order of "separator-positive electrode-separator-negative electrode-separator".

[0028] Compared with the prior art, the beneficial technical effects of the present invention are:

[0029] 1) The modified zinc material provided by the present invention is based on the specific 3D pore structure on the surface of the material, which preferentially exposes the (002) crystal plane with lower surface energy and improves the I (002) / I (100) Crystal face ratio. On the one hand, the specific microstructure can not only give the material rich electrochemical active sites and provide more nucleation sites for zinc ion deposition, but also the specific pore structure can adjust the surface crystal face ratio of the zinc material, prompting zinc ions to deposit in the horizontal direction, effectively inhibiting the growth of zinc dendrites in zinc batteries.

[0030] 2) The preparation method provided by the present invention uses aminosulfonic acid solution to etch the surface of zinc foil. Directional control of the surface microstructure of the zinc foil can be achieved by simply adjusting the solution concentration and etching time. This method is simple, low-cost, and does not produce harmful waste gas or waste liquid, making it suitable for large-scale industrial production.

[0031] 3) In the technical solution provided by the present invention, based on the specific surface structure and crystal plane ratio of the above-mentioned modified zinc material, the aqueous zinc metal battery prepared as the battery negative electrode has excellent comprehensive performance, especially by utilizing the high proportion of (002) crystal planes in the surface crystal planes of the zinc material, which can effectively inhibit the growth of zinc dendrites, thereby giving the zinc metal battery excellent cycle stability, discharge specific capacity and cycle life, which can meet the performance requirements of energy storage or power batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0033] Figure 1Schematic diagram of the preparation of modified zinc materials obtained in Examples 1 to 6 of the present invention;

[0034] Figure 2 The SEM images of the modified zinc materials obtained in Examples 1 to 6 are shown;

[0035] Figure 3 This is the SEM image of the modified zinc material obtained in Comparative Example 1;

[0036] Figure 4 The XRD patterns of the modified zinc materials obtained in Comparative Example 1 and Examples 1 to 6 are shown;

[0037] Figure 5 I is the XRD pattern of the modified zinc materials obtained in Comparative Example 1 and Examples 1 to 6. (002) / I (100) ratio cube plot;

[0038] Figure 6 A structural diagram of a button battery assembled according to the present invention;

[0039] Figure 7 The button-type symmetrical battery assembled with the modified zinc materials obtained in Comparative Example 1 and Examples 1 to 6 was tested at 1 mA cm -2 , 0.25mAh cm -2 Cyclic performance diagram under conditions;

[0040] Figure 8 The button-type symmetrical battery assembled with the modified zinc materials obtained in Comparative Example 1 and Example 3 was tested at 2 mA cm -2 , 0.5mAhcm -2 Cyclic performance diagram under conditions;

[0041] Figure 9 The button-type symmetrical battery assembled with the modified zinc materials obtained in Comparative Example 1 and Examples 1 to 6 was tested at 1 mA cm -2 , 0.25mAh cm -2 SEM images after 50 cycles under the same conditions.

[0042] Figure 10 The button-type full battery assembled with the modified zinc material obtained in Comparative Example 1 and Example 3 and the positive electrode was -1 Cyclic performance diagram under conditions;

[0043] Figure 11 The button-type full battery assembled with the modified zinc material obtained in Comparative Example 1 and Example 3 and the positive electrode was -1 Cyclic performance diagram under conditions;

[0044] Figure 12 A structural diagram of a soft-pack battery assembled according to the present invention;

[0045] Figure 13The modified zinc material obtained in Comparative Example 1 and Example 3 was assembled with the positive electrode into a soft-pack full battery at 5Ag. -1 Cyclic performance diagram under . DETAILED DESCRIPTION

[0046] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the accompanying drawings and embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0047] Example 1

[0048] This embodiment provides an ultra-thin modified zinc material with a surface 3D pore structure, and the specific preparation process is as follows:

[0049] A1. Clean the surface of 99.999% pure, 20 μm thick commercial zinc foil with anhydrous ethanol. Dry the foil in a 60°C oven.

[0050] A2. The commercial zinc foil dried in step A1 was punched into discs with a diameter of 10 mm;

[0051] A3. Add 9.709 g of sulfamic acid solid to a beaker filled with deionized water and stir at room temperature to dissolve. Transfer the solution into a 100 mL volumetric flask and dilute to volume to obtain a 1 M sulfamic acid solution.

[0052] A4. The zinc metal disc obtained in step A2 was immersed in a 1M sulfamic acid solution and maintained for 10 min;

[0053] A5. Rinse the ultra-thin modified zinc material with a preferential crystal plane obtained in step A4 three times with deionized water and anhydrous ethanol, respectively, and dry it in a 60°C oven.

[0054] The ultrathin modified zinc material with preferential crystal planes prepared in this example is denoted as SAZ@Zn-10.

[0055] Example 2

[0056] The preparation method of this embodiment is exactly the same as that of Example 1, except that in step A4, the metal zinc disc is immersed in a 1 M aminosulfonic acid solution for 20 minutes.

[0057] The ultrathin modified zinc material with preferential crystal planes prepared in this example is recorded as SAZ@Zn-20.

[0058] Example 3

[0059] The preparation method of this embodiment is exactly the same as that of Example 1, except that in step A4, the metal zinc disc is immersed in a 1 M aminosulfonic acid solution for 30 minutes.

[0060] The ultrathin modified zinc material with preferential crystal planes prepared in this example is recorded as SAZ@Zn-30.

[0061] Example 4

[0062] The preparation method of this embodiment is exactly the same as that of Example 1, except that in step A4, the metal zinc disc is immersed in a 1 M aminosulfonic acid solution for 40 minutes.

[0063] The ultrathin modified zinc material with preferential crystal planes prepared in this example is denoted as SAZ@Zn-40.

[0064] Example 5

[0065] The preparation method of this embodiment is exactly the same as that of Example 1, except that in step A4, the metal zinc disc is immersed in a 1 M aminosulfonic acid solution for 50 minutes.

[0066] The ultrathin modified zinc material with preferential crystal planes prepared in this example is denoted as SAZ@Zn-50.

[0067] Example 6

[0068] The preparation method of this embodiment is exactly the same as that of Example 1, except that in step A4, the metal zinc disc is immersed in a 1 M aminosulfonic acid solution for 60 minutes.

[0069] The ultrathin modified zinc material with preferential crystal planes prepared in this example is recorded as SAZ@Zn-60.

[0070] Comparative Example 1

[0071] The preparation method of Comparative Example 1 is exactly the same as that of Example 1, except that no immersion in sulfamic acid solution is used.

[0072] The present invention also uses the modified new material to prepare button batteries and soft-pack batteries, and conducts corresponding performance tests on them respectively. The process is as follows:

[0073] 1) Button-type symmetrical battery test

[0074] The positive and negative electrodes of the button-type symmetrical battery are the ultra-thin modified zinc material with preferential crystal planes obtained in Examples 1 to 6 and the metal zinc obtained in Comparative Example 1. The separator is filter paper, the electrolyte is 2M ZnSO4, and the amount of electrolyte used is 40 μL. Figure 6The symmetrical battery assembled with the ultrathin modified zinc materials with preferred crystal planes obtained in Examples 1 to 6 and the metal zinc negative electrode obtained in Comparative Example 1 exhibited a high conductivity at 1 mA cm -2 , 0.25mAhcm -2 The performance test data under the conditions are shown in Table 1. As can be seen from Table 1, the symmetrical battery prepared by the modified zinc material obtained in Example 3 has the best cycle stability. Further, the symmetrical battery assembled by the materials obtained in Example 3 and Comparative Example 1 is tested at 2 mA cm -2 , 0.5mAh cm -2 The cycle performance test was carried out under the following conditions, and the test data are shown in Table 1.

[0075] Table 1

[0076]

[0077] 2) Button full battery test

[0078] The positive electrode active material used in the full battery of the present invention is K 0.54 V2O5, its preparation process is:

[0079] 3.64 g of vanadium pentoxide (V2O5) and 1.26 g of oxalic acid (C2H2O4·2H2O) were added to 70 mL of deionized water (DIW) and stirred at room temperature and pressure for 10 min; 1.74 g of potassium sulfate (K2SO4) was added to the above liquid and stirred at room temperature and pressure for 30 min; the above suspension was transferred to a 100 mL polytetrafluoroethylene-lined stainless steel autoclave and hydrothermally reacted at 180°C for 48 h; after the reaction was completed, the temperature was naturally cooled, the precipitate was taken out and washed with deionized water and anhydrous ethanol three times respectively; the product (K 0.54 V2O5) was placed in a forced air drying oven at 60°C and dried overnight, and the dried block product was ground into powder to obtain the product.

[0080] The steps for preparing the positive electrode sheet used in the button-type full battery of the present invention are as follows: weigh the binder PVDF and NMP in a mass ratio of 20:1 and add them into a glass bottle, stir at room temperature for several hours until the PVDF is completely dissolved in the NMP to obtain a uniform PVDF solution with a mass fraction of 5%; weigh 210 mg of the positive electrode active material K 0.54 V2O5, 60mg of conductive agent acetylene black were placed in an agate mortar and ground thoroughly until the mixture was uniform and then placed in a glass bottle; according to the positive electrode active material K 0.54The mass ratio of V2O5, conductive agent acetylene black, and binder PVDF is required to be 7:2:1. 0.6 g of a 5% mass fraction PVDF uniform solution is added to the glass bottle in step A2, followed by 1000 μL of NMP and thorough stirring. The slurry obtained in step A3 is evenly coated on a 10 μm thick 304 stainless steel foil and dried in a vacuum oven at 50°C for 5 h. The dried positive electrode sheet is punched into discs with a diameter of 10 mm, and the mass of the positive electrode active material is weighed and calculated.

[0081] The positive electrode of the button-type full battery is the positive electrode obtained in the above steps, the negative electrode is the ultra-thin modified zinc material with preferential crystal plane obtained in Example 3 and the metal zinc obtained in Comparative Example 1, the separator is filter paper, the electrolyte is 3M ZnSO4, and the amount of electrolyte used is 45μL. Figure 6 The CR-2025 button-type full battery was assembled at room temperature in the order shown. Constant current charge and discharge tests were performed using a Blue Electric test system at a constant temperature of 30°C. The test voltage range was 0.2V to 1.6V, and the button-type full battery test current density was 5A g -1 The performance test data are shown in Table 2; the button full battery test current density is 2A g -1 The performance test data is shown in Table 2.

[0082] 3) Soft pack full battery test

[0083] The positive electrode, negative electrode, separator and electrolyte used in the soft-pack full battery of the present invention are all made of the same materials as those used in the button-type full battery. The specific dimensions differ from those of the button-type full battery as follows:

[0084] The size of the positive electrode sheet is 3cm×2cm, and the positive electrode sheet is welded to the aluminum tab. The size of the negative electrode sheet is 3.5cm×2.5cm, and the negative electrode sheet is welded to the nickel tab. The size of the diaphragm is 8cm×3.8cm. The amount of electrolyte used is 500μL.

[0085] according to Figure 12 The soft pack full battery was assembled at room temperature in the order shown. At room temperature, constant current charge and discharge tests were performed using a Xinwei battery tester. The test voltage range was 0.2V to 1.6V, and the current density of the soft pack full battery test was 5A. -1 The performance test data is shown in Table 2.

[0086] Table 2

[0087]

[0088] Depend on Figure 2It can be seen that when immersed in sulfamic acid solution of the same concentration, the number and depth of hexagonal holes on the surface of the zinc foil gradually increase with the increase of immersion time (such as Examples 1 to 6), while the surface of the metal zinc negative electrode in Comparative Example 1 is relatively flat and accompanied by cracks ( Figure 3 ). The 3D hexagonal etching morphology can preferentially expose the (002) crystal plane with lower surface energy on the zinc foil surface. From the XRD graph, it can be seen that with the increase of immersion time, the (002) crystal plane of Examples 1 to 6 gradually increases, and the XRD corresponding I (002) / I (100) The ratio first increases and then decreases and is higher than that of Comparative Example 1 (see Table 1 for details). (002) / I (100) The maximum ratio ( Figure 4-5 ), indicating that Example 3 has the strongest ability to induce horizontal deposition of zinc ions during battery cycling.

[0089] From Table 1 and Figure 7 It can be seen that the button-type symmetrical batteries assembled in Examples 1 to 6 have an average power of 1 mA cm -2 , 0.25mAh cm -2 The cycle life under the above conditions is more than 1800 hours, which is much higher than that of Comparative Example 1 (cycle life is 128 hours). Among them, Example 3 has the longest cycle life of 2428 hours.

[0090] From Table 1 and Figure 8 It can be seen that the button-type symmetrical battery assembled in Example 3 has a capacitance of 2 mA cm -2 , 0.5mAh cm -2 Under the same conditions, it can cycle for 679 hours, while the button-type symmetrical battery assembled in Comparative Example 1 can only cycle for 55 hours. Example 3 can still maintain a more stable and longer cycle life at a larger current.

[0091] Depend on Figure 9 It can be seen that the button-type symmetrical battery assembled in Comparative Example 1 has a high -2 , 0.25mAh cm -2 After 50 cycles under the same conditions, large pieces of uneven zinc deposition appeared on the electrode surface, while the electrode surface of the button-type symmetrical battery assembled in Example 3 remained flat after 50 cycles, and only zinc flakes were deposited in the horizontal direction on its electrode surface, indicating that the ultra-thin zinc negative electrode with preferential crystal planes obtained in Example 3 has excellent ability to inhibit zinc dendrites.

[0092] From Table 2 and Figure 10 It can be seen that the button-type full battery assembled in Comparative Example 1 has a short cycle life. -1 The battery was severely overcharged after only 896 cycles at a high current density of 1000 rpm, and the battery failed prematurely. The button-type full battery assembled in Example 3 failed at 5Ag. -1The cycle life is long and the discharge capacity is high at high current density. The discharge capacity is 205.1 mAh g at 2340 cycles. -1 ; From Table 2 and Figure 11 It can be seen that the button-type full battery assembled in Comparative Example 1 has a -1 The initial discharge capacity and maximum discharge capacity at the low current density of Example 3 are both smaller than those of the button-type full battery assembled in Example 3. The average discharge capacity of the button-type full battery assembled in Example 3 is 26.1 mAh g higher than that of the button-type full battery assembled in Comparative Example 1 in 500 cycles. -1 , which shows that the full battery assembled with the ultra-thin zinc negative electrode with preferential crystal plane obtained in Example 3 has a higher discharge specific capacity.

[0093] Depend on Figure 13 It can be seen that the soft pack battery assembled in Comparative Example 1 has a -1 The capacity quickly decayed under the high current density of , while the soft-pack full battery assembled in Example 3 had a long cycle life and a high discharge specific capacity (see Table 2), and the capacity retention rate after 1500 cycles was high (96.5%, vs. the initial capacity), indicating that the ultra-thin zinc negative electrode with preferential crystal plane obtained in Example 3 has great commercial potential.

[0094] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles and spirit of the present invention, and such improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An ultra-thin modified zinc material with a surface 3D pore structure, characterized by: The ratio of the (002) crystal plane to the (100) crystal plane on the surface of the zinc material is (002) / I (100) ≥1; the pore size of the 3D pore structure on the surface of the zinc material is 0.5 to 5 μm.

2. The ultra-thin modified zinc material with a surface 3D pore structure according to claim 1, characterized in that: The ratio of the (002) crystal plane to the (100) crystal plane on the surface of the zinc material is (002) / I (100) The range is 1 to 10; the thickness of the zinc material is 5 to 30 μm.

3. The ultra-thin modified zinc material with a surface 3D pore structure according to claim 1, characterized in that: The 3D pore structure on the surface of the zinc material is a multi-level hexagonal honeycomb structure with a pore diameter of 1 to 3 μm.

4. The method for preparing an ultra-thin modified zinc material with a surface 3D pore structure according to any one of claims 1 to 3, characterized in that: The metal zinc foil is cleaned and then immersed in an aminosulfonic acid solution for etching modification. After the modification is completed, it is cleaned and dried to obtain the product.

5. The method for preparing an ultra-thin modified zinc material with a surface 3D pore structure according to claim 4, characterized in that: The purity of the metal zinc foil is ≥99%; the solvent of the aminosulfonic acid solution is deionized water and / or liquid ammonia, and the concentration thereof is 0.1-1.5M.

6. The method for preparing an ultra-thin modified zinc material with a surface 3D pore structure according to claim 4, characterized in that: The solvent of the aminosulfonic acid solution is deionized water, and its concentration is 1.0-1.5M; the time of the excessive volume immersion is 10-60 minutes.

7. Use of an ultra-thin modified zinc material with a surface 3D pore structure according to any one of claims 1 to 3, characterized in that: Prepare aqueous zinc metal batteries as battery negative electrodes.

8. The use of an ultra-thin modified zinc material with a surface 3D pore structure according to claim 7, characterized in that: The aqueous zinc metal battery includes a button cell and a soft-pack cell; the button cell is composed of a positive electrode, a negative electrode, an electrolyte and a separator; the soft-pack cell is composed of a positive electrode, a negative electrode, an electrolyte, a separator, an aluminum tab and a nickel tab.

9. The use of an ultra-thin modified zinc material with a surface 3D pore structure according to claim 8, characterized in that: The positive electrode is composed of an active material, a conductive agent and a binder; the active material is at least one of a vanadium-based compound, a manganese-based compound, and a Prussian blue analogue; the conductive agent is at least one of acetylene black, Ketjen black, carbon black, graphite, carbon nanotubes and graphene; and the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene and carboxymethyl cellulose.

10. The use of an ultra-thin modified zinc material with a surface 3D pore structure according to claim 8, characterized in that: The electrolyte is at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc chloride, zinc fluoride, zinc nitrate, zinc acetate and zinc perchlorate, and its concentration is 1 to 3M; the diaphragm includes at least one of filter paper, glass fiber and hydrophilic polyolefin membrane; and the diaphragms are arranged in the order of "diaphragm-positive electrode-diaphragm-negative electrode-diaphragm".

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