Flexible high-capacity aqueous zinc battery as well as preparation method and application thereof
By constructing a three-dimensional high-load electrode on a porous three-dimensional fabric matrix and combining it with a new hydrogel electrolyte, the problems of insufficient energy density, cycle life and mechanical flexibility of aqueous zinc batteries were solved, low-cost, green large-scale preparation was achieved, and battery performance was improved.
Patent Information
- Application Number
- CN202510783181.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-12
- Publication Date
- 2025-09-19
AI Technical Summary
Existing aqueous zinc-ion batteries have shortcomings in energy density, cycle life and mechanical flexibility, and have high manufacturing costs, making it difficult to meet the needs of large-scale applications.
Screen printing technology is used to construct three-dimensional high-load electrodes on a porous three-dimensional fabric matrix. Combined with a new high-performance hydrogel electrolyte, a stable battery structure is formed at room temperature through the polymer electrolyte, realizing low-cost, green, and large-scale preparation of batteries.
It significantly improves the energy density, cycle life and mechanical flexibility of aqueous zinc batteries, reduces manufacturing costs, and provides support for flexible electronic devices and distributed energy storage systems.
Smart Images
Figure CN120674625A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of batteries, and in particular relates to a large-capacity aqueous zinc battery and a preparation method and application thereof. Background Art
[0002] As a core pillar of energy transformation, electrochemical energy storage is experiencing unprecedented development opportunities. Aqueous zinc-ion batteries, representing a new generation of safe and green batteries, offer significant advantages, including a moderate voltage window, environmentally friendly materials, and low manufacturing costs. They are one of the most commercially promising technologies after lithium-ion batteries. However, existing aqueous zinc-ion batteries still require improvement in energy density, cycle life, and mechanical flexibility. Summary of the Invention
[0003] In response to the problems existing in the existing technology, the present invention provides a large-capacity aqueous zinc battery and its preparation method and application. By innovatively designing a three-dimensional high-load electrode structure, synthesizing a new high-performance polymer electrolyte, and combining it with screen printing technology, the low-cost, green, and large-scale preparation of aqueous zinc batteries is achieved, significantly improving battery performance.
[0004] In a first aspect, the present invention provides a method for preparing a flexible large-capacity aqueous zinc battery, comprising the following steps:
[0005] S1. Using screen printing technology, print electrode slurry on a porous three-dimensional fabric substrate to prepare positive and negative electrodes;
[0006] S2. Printing a hydrogel electrolyte precursor solution onto the positive electrode and polymerizing it into a film at room temperature; the hydrogel electrolyte precursor solution is prepared from a polymer matrix, water and zinc salt;
[0007] S3. Lay the side of the positive electrode printed with the hydrogel electrolyte precursor solution on the negative electrode to obtain an aqueous zinc battery.
[0008] Furthermore, in S1, the electrode slurry includes electrode active material, carbon nanotubes, and PVDF binder in a mass ratio of (7-9): (0.5-2): (0.5-1).
[0009] Furthermore, in S1, when preparing the positive electrode, the electrode active material in the electrode slurry is one of vanadium pentoxide, sodium vanadate, and manganese dioxide; when preparing the negative electrode, the electrode active material is zinc powder.
[0010] Furthermore, in S1, when the electrode slurry is printed on the porous three-dimensional fabric substrate, the electrode active material loading is greater than 10-14 mg / cm².
[0011] In S1, porous three-dimensional fabric is used as the matrix, carbon nanotubes as the conductive network, and PVDF as the binder to form a structurally stable three-dimensional high-load electrode, and the printing construction area can reach 0.5 m².
[0012] Furthermore, in S2, the hydrogel electrolyte precursor solution comprises:
[0013] The polymer matrix is one of 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate, 3-[(3-acrylamidopropyl)dimethylammonium]propionate, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and (3-(methacrylamido)propyldimethyl(3-thiopropyl)ammonium hydroxide inner salt;
[0014] The zinc salt is one of zinc trifluoromethanesulfonate and zinc sulfate.
[0015] Furthermore, in S2, the preparation method of the hydrogel electrolyte precursor solution is:
[0016] A zinc salt solution is prepared by mixing zinc salt with water, and the zinc salt solution is added to a polymer matrix to obtain a hydrogel electrolyte precursor solution; the volume of the zinc salt solution is 10%-80% of the volume of the hydrogel electrolyte precursor solution; and the concentration of the zinc salt solution is 0.5-3 M.
[0017] Furthermore, in S2, the hydrogel electrolyte precursor solution is coated on the positive electrode and polymerized into a film at room temperature for at least 3 hours.
[0018] In a second aspect, the present invention provides an aqueous zinc battery prepared by the above preparation method.
[0019] The aqueous zinc battery comprises a positive electrode, a negative electrode, and a hydrogel electrolyte disposed between the positive and negative electrodes. Both the positive and negative electrodes are three-dimensional, high-load electrode structures. The hydrogel electrolyte is a film-forming hydrogel electrolyte precursor solution. The hydrogel electrolyte is synthesized at room temperature without requiring additional conditions. The hydrogel electrolyte is a new high-performance polymer electrolyte based on a polyzwitterionic network.
[0020] In a third aspect, the aqueous zinc battery provided by the present invention can be used in wearable devices, flexible electronic products or distributed energy storage systems.
[0021] Beneficial Effects: This invention achieves low-cost, green, and scalable production of aqueous zinc batteries through the innovative design of a three-dimensional, high-load electrode structure, the synthesis of a new high-performance polymer electrolyte, and the integration of printing technology. The battery exhibits high energy density, long cycle life, excellent mechanical flexibility, and environmental adaptability, all at a low manufacturing cost. This provides strong support for the application of aqueous zinc batteries in flexible electronic energy storage and large-scale energy storage. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 The polarization curve of the electrolyte in Example 1 and the AC impedance before and after polarization;
[0023] Figure 2 The cycle performance of the solid-state zinc battery prepared with the electrolyte in Example 2;
[0024] Figure 3 This is a physical picture of the positive electrode in Example 1;
[0025] Figure 4 This is a physical picture of the negative electrode in Example 1;
[0026] Figure 5 3 is the charge and discharge curve of the zinc battery prepared based on the prepared positive and negative electrodes and hydrogel electrolyte in Example 3;
[0027] Figure 6 This is a physical picture of the zinc battery prepared in Example 4. DETAILED DESCRIPTION
[0028] The technical solution of the present invention is described in detail below through examples, but the protection scope of the present invention is not limited to the examples. In the following examples, all raw materials can be purchased from the market.
[0029] Example 1
[0030] Step 1: Positive electrode preparation
[0031] Using vanadium pentoxide ( ) as the positive electrode active material, The positive electrode was constructed on commercially available fabric by screen printing technology, with the active material loading controlled to 10 mg cm -2 .
[0032] Step 2: Negative electrode preparation
[0033] Zinc powder (Zn) was used as the negative electrode active material. Zinc powder, carbon nanotubes, and PVDF binder were mixed in a mass ratio of 7:2:1. The negative electrode was constructed on commercially available fabric using screen printing technology, and the active material loading was controlled to 10 mg cm -2 .
[0034] Step 3: Preparation of hydrogel electrolyte:
[0035] Zinc trifluoromethanesulfonate ( ) aqueous solution was added to poly (2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate) to obtain a hydrogel electrolyte precursor solution. After the hydrogel electrolyte precursor solution was allowed to stand for 3 hours to fully polymerize, a hydrogel electrolyte was prepared. The migration number of the electrolyte was as high as 0.97 (such as Figure 1 It has excellent ion conductivity.
[0036] Among them, zinc trifluoromethanesulfonate ( ) aqueous solution in the hydrogel electrolyte precursor has a volume fraction of 20%. ) aqueous solution has a concentration of 1 M.
[0037] Step 4: Assemble the battery
[0038] The hydrogel electrolyte precursor was coated on the positive electrode surface, allowed to stand for 3 hours to fully polymerize, and then attached to the negative electrode to prepare a zinc ion battery. The battery had more than 500 cycles and a 2 A g -1 The capacity can reach 400 mAh g -1 .
[0039] Example 2
[0040] Step 1: Positive electrode preparation
[0041] Sodium vanadate ( ) is the positive electrode active material, The ratio of carbon nanotubes and PVDF binder was adjusted to 8:1:1, and a high-load positive electrode was constructed on commercially available fabrics using screen printing technology, with the active material loading increased to 11 mg cm -2 .
[0042] Step 2: Negative electrode preparation
[0043] Zinc powder (Zn) was used as the negative electrode active material. Zinc powder, carbon nanotubes, and PVDF binder were mixed in a mass ratio of 8:1:1. A high-load negative electrode was constructed on commercially available fabric using screen printing technology. The active material loading was controlled to 10 mg / cm -2 .
[0044] Step 3: Preparation of hydrogel electrolyte:
[0045] Zinc trifluoromethanesulfonate ( ) aqueous solution was added to poly (3-[(3-acrylamidopropyl) dimethylammonium] propionate) to obtain a hydrogel electrolyte precursor. After standing for 3 hours to fully polymerize, a hydrogel electrolyte was prepared. The room temperature ionic conductivity of the electrolyte was 10 mS cm -1 , with excellent ion conductivity.
[0046] Among them, zinc trifluoromethanesulfonate ( ) aqueous solution in the hydrogel electrolyte precursor has a volume fraction of 40%. Zinc trifluoromethanesulfonate ( ) The concentration of the aqueous solution is 2 M.
[0047] Step 4: Assemble the battery:
[0048] The hydrogel electrolyte precursor was coated on the positive electrode surface, and after standing for 3 hours to fully polymerize into a film, the negative electrode was attached to prepare a zinc ion battery. The zinc battery assembled with the prepared positive and negative electrodes showed a significantly higher performance than 2M zinc trifluoromethanesulfonate ( ) Aqueous electrolyte (corresponding to Figure 2 cycle life of the electrolyte).
[0049] Example 3
[0050] Step 1: Positive electrode preparation
[0051] Manganese dioxide ( ) as the positive electrode active material, , carbon nanotubes, and PVDF binder were mixed in a mass ratio of 9:0.5:0.5, and the electrode structure was constructed by screen printing technology. The active material loading was maintained at 12 mg cm -2 .
[0052] Step 2: Negative electrode preparation
[0053] Zinc powder (Zn) was used as the negative electrode active material. Zinc powder, carbon nanotubes, and PVDF binder were mixed in a mass ratio of 9:0.5:0.5. The negative electrode was constructed on commercially available fabric using screen printing technology, and the active material loading was controlled to 12 mg cm -2 .
[0054] Step 3: Preparation of hydrogel electrolyte
[0055] Zinc sulfate ( ) aqueous solution was added to poly (3-[[2 (methacryloyloxy)ethyl] dimethylammonium] propionate) to obtain a hydrogel electrolyte precursor. After standing for 3 hours to fully polymerize, a hydrogel electrolyte was prepared. The room temperature ionic conductivity of the electrolyte was 11 mS cm -1 , with excellent ion conductivity.
[0056] Among them, zinc sulfate ( ) aqueous solution in the hydrogel electrolyte precursor has a volume fraction of 60%. ) The concentration of the aqueous solution is 3M.
[0057] Step 4: Assemble the battery
[0058] The hydrogel electrolyte precursor was applied to the positive electrode surface, and after standing for 3 hours to fully polymerize, it was attached to the negative electrode to prepare a zinc ion battery. The prepared positive and negative electrodes are shown in the attached figure. Figure 3 and Figure 4 As shown, the charge and discharge curves of the assembled battery at different rates (such as Figure 5 The excellent electrochemical performance was verified.
[0059] Example 4
[0060] Step 1: Positive electrode preparation
[0061] Sodium vanadate ( ) as the positive electrode active material, The ratio of carbon nanotubes and PVDF binder was adjusted to 9:0.5:0.5, and the electrodes were prepared by screen printing technology, and the active material loading was further increased to 14 mg cm -2 .
[0062] Step 2: Negative electrode preparation
[0063] Zinc powder (Zn) was used as the negative electrode active material. Zinc powder, carbon nanotubes, and PVDF binder were mixed in a mass ratio of 9:0.5:0.5. The negative electrode was constructed on commercially available fabric using screen printing technology, and the active material loading was controlled to 14 mg cm -2 .
[0064] Step 3: Preparation of hydrogel electrolyte
[0065] Zinc trifluoromethanesulfonate ( ) aqueous solution was added to poly ((3-(methacrylamido)propyl dimethyl (3-thiopropyl) ammonium hydroxide inner salt) to obtain a hydrogel electrolyte precursor. After standing for 3 hours to fully polymerize, a hydrogel electrolyte was prepared. The room temperature ionic conductivity of the electrolyte was 9mS cm -1 , with excellent ion conductivity.
[0066] Among them, zinc trifluoromethanesulfonate ( ) aqueous solution in the hydrogel electrolyte precursor has a volume fraction of 70%. Zinc trifluoromethanesulfonate ( ) The concentration of the aqueous solution is 3M.
[0067] Step 4: Assemble the battery
[0068] The hydrogel electrolyte precursor was coated on the positive electrode surface, and after standing for 3 hours to fully polymerize, it was attached to the negative electrode to prepare a zinc ion battery. The assembled printed battery successfully powered the LED, as shown in the attached picture. Figure 6 As shown, the potential of this battery in practical applications is demonstrated.
[0069] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes may be made to the form and details without departing from the spirit and scope of the present invention.
Claims
1. A method for preparing a flexible large-capacity aqueous zinc battery, characterized in that: The steps include: S1. Using screen printing technology, print electrode slurry on a porous three-dimensional fabric substrate to prepare positive and negative electrodes; S2. Printing a hydrogel electrolyte precursor solution onto the positive electrode and polymerizing it into a film at room temperature; the hydrogel electrolyte precursor solution is prepared from a polymer matrix, water and zinc salt; S3. Lay the side of the positive electrode printed with the hydrogel electrolyte precursor solution on the negative electrode to obtain an aqueous zinc battery.
2. The preparation method according to claim 1, characterized in that In S1, the electrode slurry includes electrode active material, carbon nanotubes, and PVDF binder in a mass ratio of (7-9): (0.5-2): (0.5-1).
3. The preparation method according to claim 1, characterized in that In S1, when preparing the positive electrode, the electrode active material in the electrode slurry is one of vanadium pentoxide, sodium vanadate, and manganese dioxide; when preparing the negative electrode, the electrode active material is zinc powder.
4. The preparation method according to claim 1, characterized in that In S1, when printing the electrode slurry on the porous three-dimensional fabric substrate, the electrode active material loading is greater than 10-14 mg / cm².
5. The preparation method according to claim 1, characterized in that In S2, the hydrogel electrolyte precursor solution: The polymer matrix is one of 2-(methacryloyloxy)ethyl-2-(trimethylamino)ethyl phosphate, 3-[(3-acrylamidopropyl)dimethylammonium]propionate, 3-[[2-(methacryloyloxy)ethyl]dimethylammonium]propionate, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, and (3-(methacrylamido)propyldimethyl(3-thiopropyl)ammonium hydroxide inner salt; The zinc salt is one of zinc trifluoromethanesulfonate and zinc sulfate.
6. The preparation method according to claim 1, characterized in that In S2, the preparation method of the hydrogel electrolyte precursor solution is: preparing a zinc salt solution with water, and adding the zinc salt solution into a polymer matrix to obtain a hydrogel electrolyte precursor solution; The volume of the zinc salt solution is 10%-80% of the volume of the hydrogel electrolyte precursor solution; the concentration of the zinc salt solution is 0.5-3M.
7. The preparation method according to claim 1, characterized in that In S2, the hydrogel electrolyte precursor solution is coated on the positive electrode and polymerized into a film at room temperature for at least 3 hours.
8. An aqueous zinc battery prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the aqueous zinc battery according to claim 8 in wearable devices, flexible electronic products or distributed energy storage systems.