Method for manufacturing electrolytic zinc-manganese aqueous secondary large battery

Abstract

The invention belongs to the technical field of electrochemical energy storage, and provides a manufacturing method of an electrolytic zinc-manganese aqueous secondary large battery, which comprises a method for preparing a manganese dioxide (MnO2) positive electrode through in-situ electrochemical deposition; according to the electrolytic MnO2-Zn battery based on the Mn < 2 + > / MnO2 chemistry, higher theoretical capacity, high discharge voltage and good cycle stability are achieved, the hydroxymethyl dimethyl phosphite is adopted as an electrolyte additive, the hydrogen evolution reaction and dendritic crystal growth of a zinc negative electrode are effectively inhibited, and the service life of the battery is prolonged. The chemical reaction kinetics of an electrode-electrolyte interface is also improved, so that the cycle life and the safety of the battery are greatly improved, and meanwhile, the manganese-based positive electrode material is structurally modified, so that the problems of unstable structure and insufficient conductivity of the positive electrode material in long-term circulation are solved; therefore, the battery can still maintain a stable voltage platform and a relatively high capacity retention ratio after 3000 times of charge-discharge cycles, and the service life of the battery is remarkably prolonged.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical energy storage technology, specifically a method for manufacturing an electrolytic zinc-manganese aqueous secondary battery. Background Technology

[0002] Against the backdrop of increasing pressure on energy supply and environmental protection around the world, the research and development of large-scale energy storage technology and high-efficiency energy storage equipment is becoming increasingly important. Manganese and zinc elements are both environmentally friendly and abundant, with low cost and no biological toxicity, making them an ideal combination for building high-safety aqueous batteries. Aqueous zinc-manganese batteries have attracted much attention due to their advantages such as low cost, high power density and long cycle stability.

[0003] However, traditional Mn-based 3+ / Mn 4+ Single-electron-transfer zinc-manganese batteries still face some challenges in practical applications. For example, during charge and discharge, the unstable structure of manganese-based materials and the slow electrolytic reaction kinetics lead to decreased cycle stability and shortened lifespan. In addition, the zinc anode also suffers from dendrite growth and corrosion. Dendrites may penetrate the separator, causing internal short circuits and significantly reducing cycle life and safety. The zinc anode is also prone to hydrogen evolution during charge and discharge, which not only causes energy loss but also leads to electrolyte consumption and battery performance degradation, affecting battery efficiency and stability.

[0004] To address the problems raised in the background art, those skilled in the art have proposed a method for manufacturing an electrolytic zinc-manganese aqueous secondary large battery.

[0005] The information disclosed above in this background section is only for enhancing the understanding of the background technology of this invention, and therefore may include prior art that is not known to those skilled in the art. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a method for manufacturing an electrolytic zinc-manganese aqueous secondary large battery, thereby solving the problems of battery life degradation caused by the slow electrolytic reaction kinetics of manganese-based materials in existing zinc-manganese batteries, as well as dendrite growth and easy hydrogen evolution reaction in the negative electrode material.

[0007] To achieve the above objectives, the present invention provides a method for manufacturing an electrolytic zinc-manganese aqueous secondary battery, comprising the following steps:

[0008] S1. Using carbon felt as the positive current collector, without pre-coating with any active material, it is directly cut to the preset size. A three-electrode system is used: platinum foil as the counter electrode, Ag / AgCl as the reference electrode, and a mixed solution of 1M MnSO4 and 0.1M H2SO4 as the standard electrolyte. The electrolyte is charged to 15 mAh cm⁻¹ at a constant voltage of 1.13V. -2 The areal capacity allows the Mn in the electrolyte to... 2+ MnO2 is electrochemically deposited in situ on the surface of carbon felt, and the active material is directly generated from the electrolyte. MnO2 cathode material is electrochemically deposited in situ without coating.

[0009] S2. High-purity zinc foil is selected as the substrate, and a protective coating containing polyacrylamide polymer is introduced on its surface.

[0010] S3. Add appropriate amounts of dimethyl hydroxymethyl phosphite (HPD) and other ion regulators to the basic aqueous electrolyte, and optimize the ionic conductivity and chemical stability of the electrolyte by adjusting the pH value and ion concentration.

[0011] S4. Assemble the prepared positive electrode material, negative electrode material and prepared electrolyte into an electrolytic zinc-manganese battery.

[0012] Preferably, in the preparation process of the positive electrode material, the MnO2 positive electrode material is prepared by in-situ electrochemical deposition using a constant voltage charging method, rather than by constant current charging. Constant current charging would generate trivalent manganese ions (MnO2). 3+ This involves a single-electron transfer reaction, which affects the purity of MnO2, and this MnO2 is Mn in the electrolyte. 2+ It is deposited directly on the surface of carbon felt without the need for pre-coating.

[0013] Preferably, during the preparation of the negative electrode material, the thickness of the nanoscale protective coating is 10-100 nanometers.

[0014] Preferably, the amount of HPD added to the electrolyte is 0.1% to 5% of the total weight of the electrolyte.

[0015] Preferably, the pH value of the electrolyte is adjusted in the range of 2-4, and this acidic environment can promote the growth of Mn. 2+ / MnO2、Zn 2+ The double electron transfer reaction of / Zn is different from that of the neutral zinc-manganese battery system.

[0016] An electrolytic zinc-manganese aqueous secondary battery includes a positive electrode material, a negative electrode material, and an electrolyte.

[0017] Preferably, the positive electrode material is prepared by in-situ electrochemical deposition in a MnO2 half-cell using a standard electrolyte system of 1M MnSO4 and 0.1M H2SO4.

[0018] Preferably, the negative electrode material includes a zinc foil substrate and a protective coating disposed on its surface, the protective coating comprising a polyacrylamide polymer.

[0019] Preferably, the electrolyte is an aqueous electrolyte containing dimethyl hydroxymethyl phosphite (HPD).

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] This invention is based on Mn 2+ / MnO2 Chemistry's electrolytic MnO2-Zn battery achieves higher theoretical capacity, higher discharge voltage, and better cycle stability. By using dimethyl hydroxymethyl phosphite (HPD) as an electrolyte additive, it not only effectively inhibits the hydrogen evolution reaction and dendrite growth of the zinc anode, but also improves the chemical reaction kinetics at the electrode-electrolyte interface, thereby significantly improving the battery's cycle life and safety. At the same time, the structure of the manganese-based cathode material is modified to solve the problems of structural instability and insufficient conductivity of the cathode material during long-term cycling. As a result, the battery can maintain a stable voltage plateau and high capacity retention after 3000 charge-discharge cycles, significantly extending the battery's lifespan.

[0022] The above overview is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the invention will become readily apparent from the accompanying drawings and the following detailed description. Attached Figure Description

[0023] Figure 1 This is a schematic diagram illustrating the working principle of an electrolytic zinc-manganese aqueous secondary battery according to an embodiment of the present invention.

[0024] Figure 2 This is a microstructure characterization diagram of the electrode material of an electrolytic zinc-manganese aqueous secondary battery according to an embodiment of the present invention.

[0025] Figure 3 This is a comparison chart of the battery performance of Zn-Zn symmetric cells in the embodiments of the present invention;

[0026] Figure 4 This is a graph showing the electrochemical performance test results of the electrolytic zinc-manganese acrylic battery assembled in an embodiment of the present invention.

[0027] Figure 5 This is an assembly diagram of an electrolytic zinc-manganese aqueous secondary battery and its LED lighting test diagram according to an embodiment of the present invention.

[0028] Figure 6This is a charge-discharge characteristic curve of an electrolytic zinc-manganese aqueous secondary battery according to an embodiment of the present invention.

[0029] Figure 7 This is a diagram illustrating the electrolyte-battery interface characteristics of an electrolytic zinc-manganese aqueous secondary battery according to an embodiment of the present invention.

[0030] Figure 8 This is a schematic diagram of the assembly of a 50V 40Ah electrolytic zinc-manganese aqueous battery in an embodiment of the present invention;

[0031] Figure 9 This is a test diagram of an electric vehicle application scenario in an embodiment of the present invention;

[0032] Figure 10 This is a comparison diagram of the electrolytic zinc-manganese aqueous battery assembled in the embodiments of the present invention and a commercial lead-acid battery. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. It should be noted that the accompanying drawings are schematic and not illustrated to scale. For clarity and convenience, the relative sizes and proportions of the parts shown in the drawings have been exaggerated or reduced in size, and any size is only illustrative and not limiting.

[0034] Example 1:

[0035] Please see Figure 1 - Figure 10 As shown, an electrolytic zinc-manganese aqueous secondary battery is based on the positive electrode MnO2 / Mn 2+ and negative electrode Zn / Zn 2+ The solid-liquid phase reaction is driven by two-electron transfer, and its working principle is described as follows:

[0036] positive electrode:

[0037] E = 1.23V vs SHE

[0038] negative electrode:

[0039] E = -0.76V vs SHE

[0040] overall:

[0041] E = 1.99V vs SHE

[0042] During charging, the positive electrode is composed of Mn 2+ The deposition is MnO2 (Mn2+ →Mn 4+ The negative electrode is composed of Zn. 2+ Reduced to Zn(Zn 2+ →Zn); During discharge, Mn is ionized from solid MnO2 at the positive electrode. 2+ The negative electrode is ionized from Zn. 2+ These ionized cations return to the electrolyte, such as... Figure 1 As shown.

[0043] A method for manufacturing an electrolytic zinc-manganese aqueous secondary battery includes the following steps:

[0044] Cathode material preparation:

[0045] A carbon felt of 1mm, 3mm, or 5mm thickness (directly cut to 1cm x 1cm size, without any pre-coating) is selected as the positive electrode current collector and immersed in a 1M MnSO4 + 0.1M H2SO4 electrolyte. It is then charged at a constant voltage of 1.13V. At this point, the Mn content in the electrolyte... 2+ The MnO2 is deposited directly on the carbon felt surface by migrating to the carbon felt and losing electrons (covering the carbon fibers without cracks), replacing the traditional "coating-drying" cathode preparation process.

[0046] Anode material preparation:

[0047] Substrate selection: High-purity zinc foil is selected as the negative electrode substrate;

[0048] Preparation of protective coating: A protective coating with a thickness of about 50 nanometers is introduced on its surface by chemical plating. The coating is mainly composed of polyacrylamide polymer and other functional additives. This protective coating can effectively inhibit dendrite growth and hydrogen evolution reaction of zinc anode during charge and discharge, and improve the stability and safety of anode material.

[0049] Electrolyte preparation:

[0050] Basic electrolyte preparation: Based on aqueous electrolytes, such as zinc sulfate aqueous solution;

[0051] Additive addition: Add HPD at 2% of the total weight of the electrolyte, and add appropriate amounts of other ion regulators, such as zinc sulfate, to optimize the performance of the electrolyte;

[0052] Parameter adjustment: By adjusting the pH value of the electrolyte to around 2, it is made into an acidic state, which further improves the chemical stability and ionic conductivity of the electrolyte;

[0053] Battery assembly:

[0054] Component cutting and preparation: Cut the prepared positive electrode material and negative electrode material into appropriate sizes to ensure they match the battery casing and other components;

[0055] Assembly process: The positive electrode material, negative electrode material and prepared electrolyte are assembled together to form an electrolytic zinc-manganese battery. During the assembly process, good contact and sealing between the components are ensured to prevent electrolyte leakage and battery short circuit.

[0056] This battery does not require a pre-installed positive electrode active material layer. During the first charge, there is no MnO2 on the carbon felt surface. It is charged to 15 mAh·cm⁻¹. -2 Subsequently, a uniform MnO2 layer formed on the surface of the carbon felt, proving that the active material was directly deposited from the electrolyte. After discharge, the MnO2 dissolved into Mn. 2+ Returning to the electrolyte, no solid active material remains on the surface of the carbon felt, achieving a "deposition-dissolution" cycle;

[0057] Performance Testing: After assembly, a series of performance tests were conducted on the battery, including rate performance, cycle stability, and charge-discharge curve analysis. The test results showed that the battery performed well at 100mA / cm². 2 Even under high current density, it can maintain a stable discharge voltage platform, and after 3000 charge-discharge cycles, the capacity retention rate exceeds 90%, demonstrating good cycle stability and high current density operation capability. In addition, the internal resistance of the battery is significantly reduced, indicating that the improved interface modification technology has achieved the expected results and effectively improved the overall performance and service life of the battery.

[0058] Optimize production method

[0059] Cathode material preparation:

[0060] In a three-electrode system (i.e., a MnO2 half-cell) with carbon felt as the positive current collector, platinum foil as the counter electrode, Ag / AgCl as the reference electrode, and a mixed solution of 1M MnSO4 and 0.1M H2SO4 as the standard electrolyte, the electrolyte was charged to 15 mAh cm⁻¹ under a constant voltage of 1.13 V. -2 MnO2 cathode material was electrochemically deposited in situ under the surface capacity.

[0061] Anode material preparation:

[0062] Substrate selection and coating preparation: High-purity zinc foil was selected as the substrate, and a protective coating with a thickness of about 80 nanometers was prepared on its surface by physical vapor deposition. The coating contains polyacrylamide polymer and other components, which further enhances the protection effect on the zinc anode.

[0063] Electrolyte preparation:

[0064] Basic electrolyte and additive adjustment: Add HPD at 2% of the total weight of the basic aqueous electrolyte and add an appropriate amount of zinc nitrate as an ion regulator to adjust the pH of the electrolyte to 2 in order to improve the ionic conductivity and chemical stability of the electrolyte.

[0065] Battery assembly and testing:

[0066] Assembly process: Assemble the prepared positive and negative electrode materials and electrolyte into a battery and perform performance testing;

[0067] Test results: The battery exhibits excellent discharge voltage plateau stability at high current density. After 3500 charge-discharge cycles, the capacity retention rate is as high as 95%, demonstrating long cycle life and high safety. However, the increased cost of the battery is due to the increased thickness of the protective coating and the addition of HPD. Nevertheless, its superior performance makes it a promising candidate for applications with high requirements for battery life and safety.

[0068] Application extension creation method

[0069] Cathode material preparation:

[0070] Positive current collector optimization: carbon felt is pretreated by cleaning with PLASMA for 5 minutes or annealing in a muffle furnace at 400°C for 2 hours. This improves the specific surface area and ion transport efficiency of the material by increasing the hydrophilicity of the carbon felt and increasing the surface defects of the material.

[0071] Anode material preparation:

[0072] Flexible negative electrode preparation: A specially treated zinc-based thin film is used as the negative electrode, and its resistance to deformation is further enhanced by introducing a cross-linked polymer network, so that it can adapt to repeated bending and stretching conditions;

[0073] Electrolyte preparation:

[0074] Environmental adaptability optimization: Doping rare earth elements into the cathode material and adding antifreeze and stabilizers to the electrolyte significantly improves the battery's performance under high and low temperature conditions;

[0075] Battery assembly and testing:

[0076] Assembly process: The prepared positive and negative electrode materials and electrolyte are assembled into a flexible electrolytic zinc-manganese battery, and performance testing is performed.

[0077] Test results: Experimental verification shows that the battery can operate normally in a temperature range of -40℃ to 60℃, and the capacity decay rate is less than 5%. In addition, researchers have developed a special encapsulation material for high humidity environments, which effectively prevents moisture intrusion from affecting battery performance. These improvements enable the battery technology to be adapted to a wider range of application scenarios, including polar scientific research, aerospace and flexible wearable devices.

[0078] Example 2:

[0079] MnO2 half-cells and Zn-Cu asymmetric cells were assembled separately to investigate the morphology and structure of the deposited positive electrode MnO2 and negative electrode Zn. For the MnO2 half-cell, a carbon felt (3 mm thick, 1 cm long and 1 cm wide, immersed in the electrolyte) was used as the working electrode, an Ag / AgCl electrode as the reference electrode, and platinum foil as the counter electrode. The electrolyte was a mixed solution of 1 M MnSO4, 0.1 M H2SO4, and 0.05 M HPD. The MnO2 half-cell was charged to 15 mAh / cm³ using a constant voltage of 1.13 V. -2 The areal capacity of deposited MnO2 cathode material was obtained. Figure 2 a) The MnO2 material deposited in the optimized electrolyte system completely encapsulates the carbon fibers without cracks. The deposited MnO2 is relatively dense and has a polycrystalline structure, exposing the (211) crystal plane. Figure 2 b) The Zn-Cu asymmetric cell was assembled using zinc foil (0.08 mm thick) as the working electrode, an Ag / AgCl electrode as the reference electrode, and platinum foil (0.05 mm thick) as the counter electrode. All electrodes were immersed in the solution (each electrode had an immersion area of ​​1 cm²). -2 The Zn-Cu asymmetric cell was charged with an electrolyte consisting of a mixed solution of 1 M ZnSO4, 0.1 M H2SO4, and 0.05 M HPD at a current of 1 mA cm⁻¹. -2 The current density is charged to 15mAh cm⁻¹ -2 The areal capacity of the metal Zn electrode material deposited on the Cu substrate was obtained. Figure 2 c) The Zn deposited in the optimized electrolyte system is relatively uniform and dense. This is due to the zinc anode having few unsaturated bonds, strong interatomic energy, and low surface energy, which facilitates its continuous deposition. The uniform and dense deposition of the zinc anode plays a crucial role in mitigating dendrite formation and side reactions, thereby improving anode capacity and cycle stability. The small-angle X-ray scattering (SAXS) pattern of the zinc anode deposited in the optimized electrolyte system shows a significant scattering ring intensity. Figure 2 d) reveals its good crystallinity.

[0080] Example 3:

[0081] The Zn-Zn symmetric cell is assembled by separating two zinc foils (0.08 mm thick, φ14 diameter circular electrodes) with a glass fiber separator and using a mixed solution of 1 M ZnSO4 and 0.1 M H2SO4 as the electrolyte. The difference between the optimized and unoptimized Zn-Zn symmetric cells lies in the addition of 0.05 M HPD additive to the electrolyte in the optimized Zn-Zn symmetric cell. In-situ differential electrochemical mass spectrometry (DEMS) shows that the unoptimized Zn-Zn symmetric cell generates high-flow-rate and high-concentration H2 during cycling, while the optimized Zn-Zn cell generates significantly lower and less H2 during cycling. Figure 3 a) This reveals that the additive strategy can effectively suppress the hydrogen evolution reaction and reduce the corrosion of the zinc anode. Long-cycle testing revealed that after 100 hours of operation, the Zn-Zn battery experienced severe electrode polarization and could only operate for about 250 hours. In contrast, the Zn-Zn (optimized) battery exhibited significant long-cycle stability, operating continuously for up to 2000 hours. Figure 3 b).

[0082] Example 4:

[0083] The MnO2-Zn full cell was assembled using carbon felt as the positive electrode, zinc foil as the negative electrode, and 1M MnSO4, 1M ZnSO4, and 0.1M H2SO4 as the electrolyte. For comparison, a control battery was assembled by optimizing the electrolyte by adding 0.05M HPD solution to the standard electrolyte. After assembly, a series of electrochemical performance tests were performed, including rate performance, cycle stability, and charge-discharge curve analysis. The assembled Zn-MnO2 (optimized) battery achieved a rate performance of [value missing] at 15 mAh / cm². -2 It exhibits a high area capacity of up to 10C (100 mA cm⁻¹) -2 Rate performance (current density) Figure 4 a) Compared to the unoptimized Zn-MnO2 battery, the optimized Zn-MnO2 battery has a performance of >9mAh cm⁻¹. -2 A significant capacity improvement was observed under high surface area capacity. Figure 4 b) Zn-MnO2 (optimized) battery at 15mAh cm⁻¹ -2 Despite its high area capacity, it can still maintain a coulombic efficiency of approximately 94% and maintain stable cycling for up to 1500 cycles. Figure 4 c) In the comparison and analysis of radar charts considering five parameters (including discharge capacity, voltage plateau, cycle life, coulombic efficiency, and charging time), the Zn-MnO2 (optimized) battery exhibits superior electrochemical performance compared to the Zn-MnO2 battery. Figure 4 d).

[0084] Example 5:

[0085] Based on Example 4, the Zn-MnO2 (optimized) battery was scaled up and assembled into a 2Ah capacity pouch cell (e.g. Figure 5 As shown in the diagram, the positive electrode is made of 3mm thick carbon felt, cut into 11cm long and 8cm wide pieces; the negative electrode is made of 0.08mm thick zinc sheet, cut into 11cm long and 8cm wide pieces; glass fiber (Whatman GF / C) is used as the separator, cut into 11cm long and 8.5cm wide pieces; the positive electrode, separator, and negative electrode are assembled in sequence and electrolyte is added, and finally, the assembly is sealed with aluminum-plastic film. The assembled soft-pack battery is charged to 2Ah with a constant voltage of 2.2V. The fully charged Zn-MnO2 (optimized) soft-pack battery can light up an LED light composed of 66 diodes connected in parallel and provide a stable voltage output, ensuring reliable power supply for the Mn-Zn diode light.

[0086] Example 6:

[0087] The scaled-up, unoptimized Zn-MnO2 battery initially exhibited a discharge capacity of 0.91 Ah at a 0.5C discharge rate. After 20 cycles, the discharge capacity decreased to 0.62 Ah, and the voltage decayed to 1.45 V. The battery ceased operation by the 26th cycle. Figure 6 a and 6c), LSV test results show that the optimized electrolyte system is more conducive to the oxidation of MnO2 cathode and the reduction of zinc anode. Figure 6 b), however, the scaled-up Zn-MnO2 (optimized) pouch cell exhibited a discharge capacity exceeding 1.60 Ah at a discharge rate of 0.5C and maintained approximately 80% coulombic efficiency after 100 cycles. Figure 6 a and 6c).

[0088] Example 7:

[0089] The optimized electrolyte system exhibits higher ionic conductivity compared to the unoptimized electrolyte system, revealing that electrolyte optimization is beneficial for electron-ion transport in the battery, thereby promoting electrode reaction kinetics. Figure 7 a) Tafel testing showed that the corrosion potential of the zinc anode in the optimized electrolyte system was higher than that in the unoptimized electrolyte system, revealing that the optimized electrolyte system is beneficial to improving the corrosion resistance of the zinc anode. Figure 7 b) The relaxation time (DRT) distribution of the electrochemical impedance spectroscopy is within 10 -7 Four peaks corresponding to τ1-τ4 were displayed within a time range of up to 10 seconds. Figure 7c), where peak τ1 can be attributed to ohmic resistance (Ro), peak τ2 to contact resistance (Rc), peak τ3 to interfacial resistance (Ri), and peak τ4 to diffusion resistance (Rd). All DRT peaks of the Zn-MnO2 (unoptimized) cell are lower than those of the Zn-MnO2 (optimized) cell, especially peaks τ3 and τ4, which reveals that the additives improve electrode reaction kinetics. State of health (SOH) assessment reveals that Ri (36%) and Rd (33%) are the dominant factors in cell kinetics. Figure 7 d).

[0090] Example 8:

[0091] To verify the practical application potential of electrolytic zinc-manganese batteries, this embodiment successfully assembled a 50V 40Ah high-capacity electrolytic zinc-manganese battery. According to Embodiment 4, five 2Ah-level soft-pack batteries were assembled and connected in series to form a battery module of approximately 8V. Figure 8 a) Six 8V battery modules are installed in a Portuguese battery box with a length of 33cm, a width of 21cm, and a height of 12.5cm and connected in series to form a 50V 40Ah electrolytic zinc-manganese battery. Figure 8 b) In addition, a diverse modular design method has been developed in the battery assembly stage. This method allows individual cells to be flexibly combined into battery packs of different specifications according to actual needs, thereby meeting the needs of diverse application scenarios. Experimental results show that after adopting this design, the consistency of the battery pack has been significantly improved and the maintenance cost has been greatly reduced. This innovation has opened up a new way for the customized production of energy storage systems.

[0092] Example 9:

[0093] This embodiment also conducted a scale-up experiment on a single battery cell, assembled a 50V 40Ah electrolytic zinc-manganese battery, and applied it to the actual operation test of an electric vehicle. The test results showed that the battery exhibited good energy output capability and safety under different operating conditions, fully demonstrating its feasibility in the field of large-scale energy storage.

[0094] The national standard electric vehicle has an overall weight of approximately 25kg, a length of approximately 1.45 meters, a width of 0.64 meters, and a height of 1.05 meters. The test site's green area has a perimeter lane length of approximately 1 kilometer.

[0095] During the testing process, the electric vehicle was equipped with a 50V 40Ah electrolytic zinc-manganese battery and operated under different speeds and load conditions to comprehensively evaluate its actual performance. The test results showed that the battery maintained a stable output voltage after continuous driving for 10 kilometers, and the power consumption was highly consistent with the expected model. In particular, during uphill and acceleration scenarios, the battery demonstrated excellent instantaneous power response capabilities without significant voltage fluctuations or overheating. In addition, through real-time monitoring of the electric vehicle's operating trajectory, it was found that the battery's energy management strategy could effectively balance driving range and power output, further verifying its reliability and adaptability in practical applications. These data provide important reference for subsequent optimization of battery design and improvement of the overall performance of the electric vehicle.

[0096] All standard parts used in this invention can be purchased commercially, and irregularly shaped parts can be customized according to the description and drawings. The specific connection methods for each part all employ conventional methods such as bolts, rivets, and welding, which are mature technologies in the prior art. The machinery, parts, and equipment all use conventional models in the prior art, and the circuit connections also use conventional connection methods in the prior art, which will not be detailed here. Any content not described in detail in this specification belongs to the prior art known to those skilled in the art.

[0097] The accompanying drawings of the embodiments disclosed in this invention only involve structures related to the embodiments disclosed in this invention. Other structures can refer to general designs. In the absence of conflict, the same embodiment and different embodiments of this invention can be combined with each other.

[0098] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for manufacturing an electrolytic zinc-manganese aqueous secondary battery, characterized in that, Includes the following steps: S1. Using carbon felt as the positive current collector, without pre-coating with any active material, it is directly cut to the preset size. A three-electrode system is used: platinum foil as the counter electrode, Ag / AgCl as the reference electrode, and a mixed solution of 1M MnSO4 and 0.1M H2SO4 as the standard electrolyte. The electrolyte is charged to 15 mAh cm⁻¹ at a constant voltage of 1.13V. -2 The areal capacity allows the Mn in the electrolyte to... 2+ MnO2 is electrochemically deposited in situ on the surface of carbon felt, and the active material is directly generated from the electrolyte. MnO2 cathode material is electrochemically deposited in situ without coating. S2. High-purity zinc foil is selected as the substrate, and a protective coating containing polyacrylamide polymer is introduced on its surface. S3. Add appropriate amounts of dimethyl hydroxymethyl phosphite (HPD) and other ion regulators to the basic aqueous electrolyte, and optimize the ionic conductivity and chemical stability of the electrolyte by adjusting the pH value and ion concentration. S4. Assemble the prepared positive electrode material, negative electrode material and prepared electrolyte into an electrolytic zinc-manganese battery.

2. The method for manufacturing an electrolytic zinc-manganese aqueous secondary battery according to claim 1, characterized in that: In the preparation process of the positive electrode material, the MnO2 positive electrode material is prepared by in-situ electrochemical deposition using a constant voltage charging method, rather than constant current charging. Constant current charging would generate trivalent manganese ions (MnO2). 3+ This involves a single-electron transfer reaction, which affects the purity of MnO2, and this MnO2 is Mn in the electrolyte. 2+ It is deposited directly on the surface of carbon felt without the need for pre-coating.

3. The method for manufacturing an electrolytic zinc-manganese aqueous secondary battery according to claim 2, characterized in that: During the preparation of the negative electrode material, the thickness of the nanoscale protective coating is 10-100 nanometers.

4. The method for manufacturing an electrolytic zinc-manganese aqueous secondary battery according to claim 3, characterized in that: The amount of HPD added to the electrolyte is 0.1% to 5% of the total weight of the electrolyte.

5. The method for manufacturing an electrolytic zinc-manganese aqueous secondary battery according to claim 4, characterized in that: The pH range of the electrolyte is 2-4, and this acidic environment can promote the growth of Mn. 2+ / MnO2、Zn 2+ The double electron transfer reaction of / Zn is different from that of the neutral zinc-manganese battery system.

6. An electrolytic zinc-manganese aqueous secondary battery prepared according to any one of claims 1 to 5.

7. An electrolytic zinc-manganese aqueous secondary battery, characterized in that, It includes positive electrode materials, negative electrode materials, and electrolyte.

8. The electrolytic zinc-manganese aqueous secondary battery according to claim 7, characterized in that: The cathode material was prepared by in-situ electrochemical deposition in a MnO2 half-cell using a standard electrolyte system of 1M MnSO4 and 0.1M H2SO4.

9. The electrolytic zinc-manganese aqueous secondary battery according to claim 8, characterized in that: The negative electrode material includes a zinc foil substrate and a protective coating disposed on its surface, the protective coating comprising a polyacrylamide polymer.

10. The electrolytic zinc-manganese aqueous secondary battery according to claim 9, characterized in that: The electrolyte is an aqueous electrolyte containing dimethyl hydroxymethyl phosphite (HPD).

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