Negative electrode material for zinc ion battery, preparation method of negative electrode material, electrode and zinc ion battery

Abstract

The invention relates to the technical field of aqueous zinc ion batteries, in particular to a negative electrode material for a zinc ion battery, a preparation method of the negative electrode material, an electrode and the zinc ion battery. The preparation method of the negative electrode material for the zinc ion battery comprises the following steps: 1) soaking zinc powder in a first treatment solution for 0.5-2 hours, carrying out solid-liquid separation, and drying to obtain pretreated zinc powder; the temperature of the first treatment liquid is 0-25 DEG C; the first treatment liquid comprises a polymerization initiator and a first solvent; and 2) soaking the pretreated zinc powder in a second treatment solution for 0-2 hours or spraying a second treatment solution on the surface of the pretreated zinc powder, then reacting, carrying out solid-liquid separation, drying, and forming a functional layer on the surface of the pretreated zinc powder, the second treating fluid comprises a pyrrole monomer and a second solvent. The negative electrode material prepared by the preparation method disclosed by the invention can inhibit corrosion reaction and reduce hydrogen evolution reaction, improve the cycling stability of the zinc ion battery and prolong the service life of the zinc ion battery.

Description

Technical Field

[0001] This invention relates to the field of aqueous zinc-ion battery technology, specifically to a negative electrode material for zinc-ion batteries, its preparation method, an electrode, and a zinc-ion battery. Background Technology

[0002] Aqueous zinc-ion batteries possess advantages such as high safety, environmental friendliness, and high energy density, making them a promising next-generation energy storage battery. Furthermore, metallic zinc, the negative electrode material for zinc-ion batteries, has unique advantages, including a high theoretical capacity (5855 mAh·cm³). -3 820mAh·g -1 The zinc anode has a low redox potential (-0.762V compared to the standard hydrogen electrode), high zinc abundance (>4 times that of Li), and low cost. However, dendrite growth and hydrogen evolution reactions occur at the zinc anode, which severely hinder the reversibility and cycle stability of aqueous zinc-ion batteries.

[0003] Currently, zinc foil is mainly used as the negative electrode in zinc-ion batteries. To address the key problems of zinc negative electrodes, researchers have proposed many improvement measures, including zinc metal alloying, membrane functionalization, electrolyte optimization, and surface coating. These strategies have suppressed dendrite growth and hydrogen evolution reaction to a certain extent, thus improving the cycle performance of zinc negative electrodes. However, their inherent defects still cannot be solved: (1) dendrites spontaneously form along the vertical direction due to the two-dimensional planar structure; (2) excessively thick zinc foil leads to poor energy density; (3) the production technology of ultra-thin zinc foil is difficult; (4) as both working electrode and current collector, zinc foil is severely pulverized under high current.

[0004] Compared to zinc foil, zinc powder offers advantages such as lower cost, greater scalability, and better adjustability, making it a promising industrial production material. More importantly, the use of zinc powder avoids the drawbacks of planar zinc foil and allows for better control of the load, which is crucial for balancing the quality of the anode and cathode. Furthermore, the high surface area of ​​zinc powder can reduce the surface current density during charging and discharging, thereby lowering overpotential. However, the zinc powder anode material currently used in zinc-ion batteries is prone to anode corrosion, resulting in poor cycle life. Summary of the Invention

[0005] To address the shortcomings of the aforementioned zinc powder anode materials, the present invention aims to provide an anode material for zinc-ion batteries, its preparation method, electrode, and zinc-ion battery, which can suppress the corrosion reaction of zinc powder anodes and improve the cycle performance and service life of zinc-ion batteries.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A method for preparing a negative electrode material for zinc-ion batteries includes the following steps:

[0008] 1) Soak zinc powder in the first treatment solution for 0.5-2 hours, separate the solid and liquid, and dry to obtain pretreated zinc powder; the temperature of the first treatment solution is 0-25℃; the first treatment solution includes a polymerization initiator and a first solvent;

[0009] 2) Soak the pretreated zinc powder in the second treatment for 0-2 hours or spray the second treatment liquid onto the surface of the pretreated zinc powder, then react, separate the solid and liquid, dry, and form a functional layer on the surface of the pretreated zinc powder to obtain the negative electrode material for zinc-ion batteries; the second treatment liquid includes pyrrole monomer and a second solvent.

[0010] Furthermore, the polymerization initiator is at least one selected from ammonium persulfate, potassium persulfate, sodium dodecyl sulfate, and 68 wt% nitric acid.

[0011] Furthermore, the first solvent is either water or ethanol.

[0012] Further, in the first treatment solution, the ratio of the first solvent to the polymerization initiator is: 1-5g of polymerization initiator is used for every 50mL of the first solvent. More preferably, in the first treatment solution, the ratio of the first solvent to the polymerization initiator is: 1.3418g of polymerization initiator is used for every 50mL of the first solvent.

[0013] Furthermore, the first treatment solution further includes hexadecyltrimethylammonium bromide (CTAB). The ratio of the first solvent to CTAB in the first treatment solution is 1-5 mg of CTAB per 50 mL of the first solvent. More preferably, the ratio of the first solvent to CTAB in the first treatment solution is 1.5 mg of CTAB per 50 mL of the first solvent. In preparing the first treatment solution, the polymerization initiator is first added to water and stirred for 1-2 hours. After stirring, CTAB is added and the solution is sonicated for 1-2 hours.

[0014] Further, in step 2), the pretreated zinc powder surface is sprayed with the second treatment liquid and then left to stand for 2-8 hours.

[0015] Further, in step 2), the pretreated zinc powder is soaked, filtered, and then left to stand for 2-8 hours.

[0016] Furthermore, the second solvent is at least one of water and ethanol.

[0017] Further, in the second treatment solution, the ratio of the second solvent to the pyrrole monomer is: 0.8-2 mL of pyrrole monomer is used for every 50 mL of the second solvent. More preferably, in the second treatment solution, the ratio of the second solvent to the pyrrole monomer is: 1.26 mL of pyrrole monomer is used for every 50 mL of the second solvent.

[0018] Furthermore, the second treatment solution also includes CTAB. The ratio of the second solvent to CTAB in the second treatment solution is: 1-5 mg of CTAB per 50 mL of the second solvent. More preferably, the ratio of the second solvent to CTAB in the second treatment solution is: 1.5 mg of CTAB per 50 mL of the second solvent.

[0019] Furthermore, the second treatment solution also includes at least one of zirconium oxynitrate solution, zirconium sulfate solution, and zirconium nitrate solution. Specifically, taking zirconium oxynitrate solution as an example, the concentration of zirconium oxynitrate solution in the second treatment solution is 10-30 mg / mL. Preferably, the concentration of zirconium oxynitrate solution in the second treatment solution is 20 mg / mL.

[0020] Further, in step 2), after spraying the pretreated zinc powder surface with the second treatment liquid, the process further includes drying and spraying with a third treatment liquid; or, after immersing the pretreated zinc powder in the second treatment liquid for 0-2 hours, the process further includes filtering, drying, and then immersing, filtering, and drying with the third treatment liquid; the third treatment liquid includes at least one of zirconium oxynitrate solution, zirconium sulfate solution, and zirconium nitrate solution, along with a third solvent.

[0021] Furthermore, the third solvent is at least one of water and ethanol.

[0022] Further, the third treatment solution comprises a zirconium oxynitrate solution and a third solvent. The ratio of the third solvent to the zirconium oxynitrate solution in the third treatment solution is: 10-40 mg of zirconium oxynitrate per 100 mL of the third solvent. More preferably, 15 mg of zirconium oxynitrate is used per 100 mL of the third solvent.

[0023] Furthermore, the third treatment solution also includes CTAB. In the third treatment solution, the ratio of the third solvent to CTAB is: 3-6 mg of CTAB per 120 mL of the third solvent. More preferably, the ratio of the third solvent to CTAB in the third treatment solution is: 4 mg of CTAB per 120 mL of the third solvent.

[0024] Furthermore, after spraying with the third treatment liquid, the process includes drying and spraying with the fourth treatment liquid; or, after soaking, filtering, and drying with the third treatment liquid, the process includes soaking, filtering, and drying with the fourth treatment liquid; the fourth treatment liquid includes reduced graphene oxide and a fourth solvent.

[0025] Further, in the fourth treatment solution, the ratio of the fourth solvent to the reduced graphene oxide is: 20 mg of reduced graphene oxide is used per 100 mL of the fourth solvent. Further, the fourth treatment solution also includes at least one of zirconium oxynitrate, zirconium sulfate, and zirconium nitrate, more preferably zirconium oxynitrate. The ratio of the fourth solvent to zirconium oxynitrate is: 10-40 mg of zirconium oxynitrate is used per 100 mL of the fourth solvent.

[0026] Furthermore, the fourth treatment solution also includes pyrrole monomer. The ratio of the fourth solvent to pyrrole monomer in the fourth treatment solution is: 1-2 mL of pyrrole monomer per 100 mL of the fourth solvent. Further, the ratio of the fourth solvent to pyrrole in the fourth treatment solution is: 1.2 mL of pyrrole monomer per 120 mL of the fourth solvent. Further, the fourth treatment solution also includes an initiator.

[0027] Furthermore, the fourth solvent is at least one of water and ethanol.

[0028] Furthermore, after spraying with the fourth treatment liquid, the process further includes drying and spraying with the fifth treatment liquid; or, after soaking, filtering, and drying with the fourth treatment liquid, the process further includes soaking, filtering, and drying with the fifth treatment liquid; the fifth treatment liquid includes at least one of zirconium oxynitrate, zirconium sulfate, and zirconium nitrate.

[0029] Furthermore, the fifth treatment solution includes zirconium oxynitrate.

[0030] Further, in the fifth treatment solution, the ratio of the fifth solvent to zirconium oxynitrate is: 10-50 mg of zirconium oxynitrate is used for every 50 mL of the fifth solvent. More preferably, 40 mg of zirconium oxynitrate is used for every 50 mL of the fifth solvent.

[0031] Furthermore, the fifth treatment solution also includes polypyrrole. In the fifth treatment solution, the ratio of the fifth solvent to polypyrrole is: 10-50 mg of polypyrrole per 50 mL of the fifth solvent. More preferably, 15 mg of polypyrrole is used per 50 mL of the fifth solvent.

[0032] Alternatively, the preparation method of the negative electrode material for zinc-ion batteries includes the following steps:

[0033] 1) Soak zinc powder in a first treatment solution for 0.5-2 hours, separate the solid and liquid, and dry to obtain pretreated zinc powder; the temperature of the first treatment solution is 0-25℃; the first treatment solution includes at least one of zirconium oxynitrate, zirconium sulfate, and zirconium nitrate in a first solvent;

[0034] 2) Soak the pretreated zinc powder in the second treatment for 0-2 hours or coat the surface of the pretreated zinc powder with the second treatment liquid, react, separate the solid and liquid, dry, and form a functional layer on the surface of the pretreated zinc powder to obtain the negative electrode material for zinc-ion batteries; the second treatment liquid includes pyrrole monomer, polymerization initiator, and second solvent.

[0035] Furthermore, the polymerization initiator is at least one selected from ammonium persulfate, potassium persulfate, sodium dodecyl sulfate, and 68% nitric acid.

[0036] Furthermore, the first solvent is at least one of water and ethanol.

[0037] Further, the ratio of the first solvent to the polymerization initiator in the first treatment solution is 1-5g of polymerization initiator per 50ml of the first solvent. Preferably, the ratio of the first solvent to the polymerization initiator in the first treatment solution is 1.3418g of polymerization initiator per 50ml of the first solvent.

[0038] Furthermore, the first treatment solution also includes CTAB. The ratio of the first solvent to CTAB in the first treatment solution is 1-5 mg of CTAB per 50 ml of the first solvent. Preferably, the ratio of the first solvent to CTAB in the first treatment solution is 1.5 mg of CTAB per 50 ml of the first solvent. In preparing the first treatment solution, the polymerization initiator is first added to water and stirred for 1-2 hours. After stirring, CTAB is added, and the solution is sonicated for 1-2 hours.

[0039] Further, in step 2), the pretreated zinc powder surface is sprayed with the second treatment liquid and then left to stand for 2-8 hours.

[0040] Further, in step 2), the pretreated zinc powder is soaked, filtered, and then left to stand for 2-8 hours.

[0041] Further, the second solvent is at least one of water and ethanol. The ratio of the second solvent to pyrrole monomer in the second treatment solution is 0.8-2 mL of pyrrole monomer per 50 mL of the second solvent. Preferably, the ratio of the second solvent to pyrrole monomer in the second treatment solution is 1.26 mL of pyrrole monomer per 50 mL of the second solvent.

[0042] Furthermore, the second treatment solution also includes CTAB. The ratio of the second solvent to CTAB in the second treatment solution is 1-5 mg of CTAB per 50 mL of the second solvent. Preferably, the ratio of the second solvent to CTAB in the second treatment solution is 1.5 mg of CTAB per 50 mL of the second solvent.

[0043] Further, in step 2), after the pretreated zinc powder surface is sprayed with the second treatment solution and dried, it is then sprayed with the third treatment solution. Alternatively, in step 2), the pretreated zinc powder is immersed in the second treatment solution, filtered, and dried, and then immersed in the third treatment solution, filtered, and dried.

[0044] Furthermore, the third treatment solution includes at least one of zirconium oxynitrate solution, zirconium sulfate solution, and zirconium nitrate solution, along with a third solvent. The third solvent is at least one of water and ethanol.

[0045] Furthermore, the ratio of the third solvent to the zirconium oxynitrate solution in the third treatment solution is 10-40 mg of zirconium oxynitrate per 100 ml of the third solution. Preferably, the ratio of the third solvent to the zirconium oxynitrate solution in the third treatment solution is 15 mg of zirconium oxynitrate per 100 ml of the third solvent.

[0046] Furthermore, the third treatment solution also includes CTAB. The ratio of the third solvent to CTAB in the third treatment solution is 3-6 mg of CTAB per 120 mL of the third solvent. Preferably, the ratio of the third solvent to CTAB in the third treatment solution is 4 mg of CTAB per 120 mL of the third solvent.

[0047] Furthermore, after the pretreated zinc powder is sprayed with a third treatment solution and dried, a fourth treatment solution is applied. Alternatively, the pretreated zinc powder is immersed in the third treatment solution, filtered, and dried, then immersed in the fourth treatment solution, filtered, and dried.

[0048] Furthermore, the fourth processing liquid includes pyrrole monomer, polymerization initiator, and third solvent.

[0049] Furthermore, the polymerization initiator is at least one selected from ammonium persulfate, potassium persulfate, sodium dodecyl sulfate, and 68% nitric acid.

[0050] Furthermore, the fourth processing solution includes reduced graphene oxide and a fourth solvent. Preferably, the ratio of the fourth solvent to reduced graphene oxide in the fourth processing solution is 20 mg of reduced graphene oxide per 100 mL of the fourth solvent.

[0051] Furthermore, after spraying the pretreated zinc powder surface with the fourth treatment solution and drying it, a fifth treatment solution is applied. Alternatively, the pretreated zinc powder is immersed in the fourth treatment solution, filtered, and dried, then immersed in the fifth treatment solution, filtered, and dried.

[0052] Further, the fifth treatment solution includes at least one of zirconium oxynitrate, zirconium sulfate, and zirconium nitrate. Zirconium oxynitrate is preferred. The ratio of the fifth solvent to zirconium oxynitrate in the fifth treatment solution is 10-50 mg of zirconium oxynitrate per 50 ml of the fifth solvent. Preferably, the ratio of the fifth solvent to zirconium oxynitrate in the fifth treatment solution is 40 mg of zirconium oxynitrate per 50 ml of the fifth solvent.

[0053] Furthermore, the fifth treatment solution also includes polypyrrole. The ratio of the fifth solvent to polypyrrole in the fifth treatment solution is 10-50 mg of polypyrrole per 50 ml of the fifth solvent. Preferably, the ratio of the fifth solvent to polypyrrole in the fifth treatment solution is 15 mg of polypyrrole per 50 ml of the fifth solvent.

[0054] Furthermore, the solvent for the fifth treatment solution is at least one of water and ethanol.

[0055] Furthermore, the fifth treatment solution is a mixture of water and anhydrous ethanol in a volume ratio of 1:1.

[0056] A negative electrode material for zinc-ion batteries prepared by the above-described method.

[0057] An electrode using the aforementioned negative electrode material for zinc-ion batteries.

[0058] A zinc-ion battery includes a positive electrode, a negative electrode, and a separator, wherein the negative electrode is the aforementioned electrode.

[0059] Furthermore, the positive electrode includes a positive electrode current collector and a positive electrode material layer disposed on the surface of the positive electrode current collector. The positive electrode material layer includes a positive electrode active material, a conductive agent, and a positive electrode binder. The positive electrode active material is vanadium pentoxide.

[0060] The beneficial effects of this invention are:

[0061] This invention provides a method for preparing a negative electrode material for zinc-ion batteries. The modified zinc powder negative electrode obtained can inhibit corrosion reactions and reduce hydrogen evolution reactions, thereby improving the cycle stability and service life of zinc-ion batteries. Furthermore, the method of this invention has a simple preparation process and low environmental requirements. Attached Figure Description

[0062] Figure 1 This is a SEM image of the zinc-ion battery negative electrode material prepared in Example 1;

[0063] Figure 2 This is a SEM image of the zinc-ion battery negative electrode material prepared in Example 2;

[0064] Figure 3 The infrared spectrum of the zinc-ion battery anode material prepared in Example 1 is shown below.

[0065] Figure 4 The charge-discharge test curve of the zinc-ion battery negative electrode material prepared in Example 1 at 1A / g;

[0066] Figure 5 The charge-discharge test curve of the zinc-ion battery negative electrode material prepared in Example 1 at 3A / g;

[0067] Figure 6 The negative electrode material for zinc-ion batteries prepared in Example 2 is at 0.2 mA / cm 2 The cyclic test curve;

[0068] Figure 7 The negative electrode material for zinc-ion batteries prepared in Example 2 is at 0.5 mA / cm 2 The cyclic test curve;

[0069] Figure 8 The negative electrode material for zinc-ion batteries prepared in Example 2 is at 1.0 mA / cm 2 The cyclic test curve. Detailed Implementation

[0070] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments and test examples. However, those skilled in the art should understand that the embodiments are only used to illustrate the technical solution of the present invention and should not be regarded as limiting the scope of protection of the present invention.

[0071] Example 1

[0072] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0073] 1) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0074] 2) Add 10g of zinc powder to the dispersion solution prepared in step 1), and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0075] 3) Add 1.3418g of 68% nitric acid to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0076] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0077] The method for preparing the zinc-ion battery in this embodiment includes the following steps:

[0078] 1) Mix V2O5 powder with Super P and PVDF binder in a mass ratio of 7:2:1, then grind evenly, add an appropriate amount of NMP solvent, and stir at room temperature for 24 hours to obtain V2O5 positive electrode slurry;

[0079] 2) Coat the positive electrode slurry onto the positive electrode current collector, dry, roll, and cut to obtain the positive electrode sheet.

[0080] 3) Using zinc foil as the negative electrode, the positive electrode, separator, the zinc-ion battery negative electrode material prepared above, electrolyte, and shell are assembled, injected, sealed, and activated to prepare a zinc-ion battery.

[0081] Example 2

[0082] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0083] 1) Add 1.3418g of 68% nitric acid to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0084] 2) Add 10g of zinc powder to the mixture obtained in step 1) and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0085] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0086] 4) Add the soaking solution obtained in step 2) to the dispersion solution in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0087] The preparation method of the zinc-ion battery in this embodiment is the same as that in Embodiment 1.

[0088] Example 3

[0089] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0090] 1) Add 1.3418g of 68% nitric acid to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0091] 2) Add 10g of zinc powder to the mixture obtained in step 1) and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0092] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0093] 4) Add the soaking solution obtained in step 2) to the dispersion solution in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0094] The preparation method of the zinc-ion battery in this embodiment is the same as that in Embodiment 1.

[0095] Example 4

[0096] The difference between this embodiment and embodiment 3 is that in step 4) of preparing the negative electrode material, the soaking solution obtained in step 2) is filtered, dried in a vacuum drying oven at 50°C for 6 hours to obtain pretreated zinc powder. Then, the pyrrole dispersion solution obtained in step 3) is sprayed onto the pretreated zinc powder obtained in step 2), filtered, repeatedly rinsed with deionized water, and then dried in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0097] Example 5

[0098] 1) Add 1.6g of 68% nitric acid to 70ml of deionized water, stir for 2h, add 2.5mg of CTAB, and then sonicate for 50min to form a mixture;

[0099] 2) Add 15g of zinc powder to the mixture prepared in step 1 and soak at 3°C ​​for 50 minutes.

[0100] 3) Add the soaking solution obtained in step 2) to the mixture obtained in step 1), stir at room temperature for 4 hours, filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0101] Example 6

[0102] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0103] 1) Add 1.5 mL of pyrrole monomer to 60 mL of deionized water and stir for 1.5 h to obtain a uniform dispersion solution;

[0104] 2) Add 12g of zinc powder to the dispersion solution prepared in step 1), and soak at 10℃ for 20 minutes to obtain the soaking solution;

[0105] 3) Add 1.5g of 68% nitric acid to 60mL of deionized water, stir for 1.5h, add 2.0mg of CTAB, and then sonicate for 20min to form a mixture;

[0106] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), stir, and polymerize at room temperature for 3 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 60°C for 10 hours to obtain the final product.

[0107] Example 7

[0108] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0109] 1) Add 1.8 mL of pyrrole monomer to 70 mL of deionized water and stir for 1 h to disperse evenly to obtain a dispersion solution;

[0110] 2) Add 15g of zinc powder to the dispersion solution prepared in step 1), and soak at 15℃ for 15 minutes to obtain the soaking solution;

[0111] 3) Add 2.0g of 68% nitric acid to 70mL of deionized water, stir for 0.5h, add 3.0mg of CTAB, and then sonicate for 15min to form a mixture;

[0112] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), then stir and polymerize at room temperature for 2 hours.

[0113] Filter, then rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 70°C for 8 hours to obtain the final product.

[0114] Example 8

[0115] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0116] 1) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0117] 2) Add 10g of zinc powder to the dispersion solution prepared in step 1), and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0118] 3) Add 0.5g of zirconium oxynitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0119] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0120] Example 9

[0121] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0122] 1) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0123] 2) Add 10g of zinc powder to the dispersion solution prepared in step 1), and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0124] 3) Add 0.5g of zirconium sulfate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0125] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0126] Example 10

[0127] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0128] 1) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion solution;

[0129] 2) Add 10g of zinc powder to the dispersion solution prepared in step 1), and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0130] 3) Add 0.5g of zirconium nitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0131] 4) Add the soaking solution obtained in step 2) to the mixture in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0132] Example 11

[0133] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0134] 1) Add 0.5g of zirconium oxynitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0135] 2) Add 10g of zinc powder to the mixture obtained in step 1) and soak at 5℃ for 30 minutes to obtain the soaking solution;

[0136] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0137] 4) Add the soaking solution obtained in step 2) to the dispersion in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the product.

[0138] Example 12

[0139] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0140] 1) Add 0.5g of zirconium nitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0141] 2) Add 10g of zinc powder to the mixture obtained in step 1), soak at 5℃ for 30 minutes, and filter to obtain the treated zinc powder;

[0142] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0143] 4) Add the treated zinc powder obtained in step 2) to the dispersion in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0144] Example 13

[0145] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0146] 1) Add 0.5g of zirconium sulfate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0147] 2) Add 10g of zinc powder to the mixture obtained in step 1), soak at 5℃ for 30 minutes, and filter to obtain the treated zinc powder;

[0148] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0149] 4) Add the treated zinc powder obtained in step 2) to the dispersion in step 3), stir, and polymerize at room temperature for 4 hours. Filter, rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0150] Example 14

[0151] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0152] 1) Add 0.5g of zirconium oxynitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0153] 2) Add 10g of zinc powder to the mixture obtained in step 1), soak at 5℃ for 30min, filter, and dry in a vacuum drying oven at 50℃ for 6h to obtain treated zinc powder.

[0154] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0155] 4) Spray the dispersion obtained in step 3) onto the treated zinc powder obtained in step 2), filter it, rinse it repeatedly with deionized water, and then dry it in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0156] Example 15

[0157] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0158] 1) Add 0.5g of zirconium nitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form a mixture;

[0159] 2) Add 10g of zinc powder to the mixture obtained in step 1), soak at 5℃ for 30min, filter, and dry in a vacuum drying oven at 50℃ for 6h to obtain treated zinc powder.

[0160] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0161] 4) Spray the dispersion obtained in step 3) onto the treated zinc powder obtained in step 2), filter it, rinse it repeatedly with deionized water, and then dry it in a vacuum drying oven at 50°C for 12 hours to obtain the final product.

[0162] Example 16

[0163] The method for preparing the negative electrode material for zinc-ion batteries in this embodiment includes the following steps:

[0164] 1) Add 0.5g of zirconium oxynitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form mixture A;

[0165] 2) Add 10g of zinc powder to the mixture obtained in step 1), soak at 5℃ for 30min, filter, and dry in a vacuum drying oven at 50℃ for 6h to obtain treated zinc powder.

[0166] 3) Add 1.26 mL of pyrrole monomer to 50 mL of deionized water and stir for 2 hours to obtain a uniform dispersion.

[0167] 4) Spray the dispersion obtained in step 3) onto the treated zinc powder obtained in step 2), and then spray the initiator solution. The initiator solution is obtained by mixing 2.28g of ammonium persulfate with 20mL of deionized water. Filter the solution, rinse it repeatedly with deionized water, and then dry it in a vacuum drying oven at 50℃ for 12h to obtain functional zinc powder.

[0168] 5) Add 0.5g of zirconium oxynitrate to 50mL of deionized water, stir for 1h, add 1.5mg of CTAB, and then sonicate for 30min to form mixture B; spray mixture B onto the surface of the functional zinc powder prepared in step 4); filter, then rinse repeatedly with deionized water, and then dry in a vacuum drying oven at 50℃ for 12h to obtain the final product.

[0169] (1) Physicochemical tests

[0170] The negative electrode material prepared in Example 1 was subjected to scanning electron microscopy (SEM) testing. The test results are shown in [Figure 1]. Figure 1 .

[0171] The negative electrode material prepared in Example 2 was subjected to scanning electron microscopy (SEM) testing. The test results are shown in [Figure 1]. Figure 2 .

[0172] from Figure 1 It can be seen that the zinc powder is coated with a layer of polypyrrole modified material (PPy).

[0173] from Figure 2 It can be seen that the zinc powder is coated with a layer of polypyrrole material (PPy).

[0174] The negative electrode material prepared in Example 1 was subjected to infrared spectral characteristic peak testing, and the results are as follows: Figure 3 As shown.

[0175] Depend on Figure 3 It can be seen that the zinc powder of the present invention is successfully coated with a layer of polypyrrole.

[0176] (2) Charge and discharge test

[0177] The negative electrode material obtained in Example 1 was used to prepare a zinc-ion battery according to the method in Example 1, and charge-discharge tests were performed. The charge-discharge mechanism was as follows: charge-discharge tests were performed in the blue battery system under the conditions of current density of 1 A / g and 3 A / g and voltage range of 0.25-1.6V.

[0178] The charge-discharge test results at current densities of 1 A / g and 3 A / g are as follows: Figure 4 and Figure 5 As shown. By Figure 4 and Figure 5 It can be seen that the negative electrode material of the present invention has excellent charge and discharge performance.

[0179] (3) Cyclic performance test

[0180] Using the negative electrode material (Zn@PPy) obtained in Example 2, and comparing it with ordinary zinc powder (Zn=p) and zinc foil (Zn-foil), a zinc-ion battery was prepared according to the preparation method of a symmetrical battery, and charge-discharge cycle tests were performed. The charge-discharge mechanism was as follows: at a current density of 0.2 mA / cm²... -2 0.5mAcm -2 1mAcm -2 The following charge-discharge cycle test was performed, and the results are as follows: Figure 6 , 7 As shown in Figure 8.

[0181] Depend on Figure 6 , 7 As can be seen from 8, the negative electrode material prepared by this invention can effectively improve the cycle life of the battery compared with ordinary zinc powder and zinc foil.

[0182] Although the technical solution of the present invention has been described in detail above with general descriptions, specific embodiments, and experimental examples, it should be noted that the embodiments and experimental examples are only used to illustrate the technical solution and technical effects of the present invention, and should not be regarded as any limitation on the scope of protection of the present invention. Simple modifications, alterations, or improvements made based on the technical concept of the present invention are all within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a negative electrode material for a zinc ion battery, characterized by, The method comprises the following steps: 1) soaking zinc powder in a first treatment liquid for 0.5-2h, solid-liquid separation, drying, to obtain pretreated zinc powder; the temperature of the first treatment liquid is 0-25℃; the first treatment liquid comprises a polymerization initiator and a first solvent; 2) soaking the pretreated zinc powder in a second treatment liquid for 0-2h or spraying the second treatment liquid on the surface of the pretreated zinc powder, then reacting, solid-liquid separation, drying, to form a functional layer on the surface of the pretreated zinc powder, to obtain the negative electrode material for zinc ion battery.

2. The method of producing a negative material for a zinc ion battery according to claim 1, characterized by, In the first treatment liquid, the ratio of the first solvent to the polymerization initiator is: 1-5g of the polymerization initiator corresponds to 50mL of the first solvent.

3. The method of producing a zinc-ion battery anode material according to claim 1, wherein, In the second treatment liquid, the ratio of the second solvent to the pyrrole monomer is: 0.8-2mL of the pyrrole monomer corresponds to 50mL of the second solvent.

4. The method of producing a negative material for a zinc ion battery according to claim 1, characterized by, The second treatment liquid further comprises at least one of a zirconium oxynitrate solution, a zirconium sulfate solution, and a zirconium nitrate solution.

5. The method of producing a negative material for a zinc ion battery according to claim 1, characterized by, In step 2), after the pretreated zinc powder is sprayed with the second treatment liquid, the method further comprises the steps of drying and spraying with a third treatment liquid; or, after the pretreated zinc powder is soaked in the second treatment liquid for 0-2h, the method further comprises the steps of filtering, drying, soaking in a third treatment liquid, filtering, and drying; the third treatment liquid comprises at least one of a zirconium oxynitrate solution, a zirconium sulfate solution, and a zirconium nitrate solution and a third solvent.

6. The method of producing a negative material for a zinc-ion battery according to claim 5, characterized by, After spraying with the third treatment liquid, the method further comprises the steps of drying and spraying with a fourth treatment liquid; or, after soaking in the third treatment liquid, filtering, and drying, the method further comprises the steps of soaking in a fourth treatment liquid, filtering, and drying; the fourth treatment liquid comprises reduced graphene oxide and a fourth solvent.

7. The method of producing a negative material for a zinc-ion battery according to claim 6, characterized by, After spraying with the fourth treatment liquid, the method further comprises the steps of drying and spraying with a fifth treatment liquid; or, after soaking in the fourth treatment liquid, filtering, and drying, the method further comprises the steps of soaking in a fifth treatment liquid, filtering, and drying; the fifth treatment liquid comprises at least one of a zirconium oxynitrate solution, a zirconium sulfate solution, and a zirconium nitrate solution.

8. A negative electrode material for zinc ion battery prepared by the method of any one of claims 1-7.

9. An electrode using the negative electrode material for zinc ion battery of claim 8.

10. A zinc-ion battery comprising a positive electrode, a negative electrode, a separator, characterized in that, The negative electrode is the electrode of claim 9.

Images