A high capacity zinc-manganese battery

Abstract

The invention relates to a high-capacity zinc-manganese battery, which adopts a multi-layer stacked negative electrode structure to improve the energy density and total capacity of the battery. The negative electrodes are effectively isolated by a first separator and a second separator to prevent short circuit, and are activated layer by layer when different negative electrodes are exhausted, thereby extending the battery life. The positive electrode adopts a tubular hollow structure and is filled with manganese dioxide active material. Fins are provided at both the inner and outer ends to increase the contact area between the active material and the electrolyte, thereby improving the electrochemical reaction efficiency. An intelligent electrolyte management system includes pH-responsive microcapsule technology. Concentrated electrolyte is stored inside the microcapsule, and is automatically released and replenished according to changes in electrolyte concentration during battery discharge, thereby maintaining a suitable electrolyte concentration and ensuring stable battery performance. In addition, a separator made of elastic insulating material and a buffer chamber pre-filled with inert gas are provided between the collector and the positive electrode, thereby enhancing the safety and pressure resistance stability of the battery.

Description

Technical Field

[0001] The present invention relates to a high-capacity zinc-manganese battery, in particular to a high-capacity zinc-manganese battery applied in the technical field of high-capacity zinc-manganese batteries. Background Art

[0002] Chinese invention patent CN114628708 discloses a mercury-free, lead-free, cadmium-free zinc-manganese battery. By replacing traditional harmful heavy metals with metal elements such as magnesium, titanium, tin, indium, and bismuth, the safety and environmental friendliness of the battery are significantly improved, and the battery performance is improved by optimizing the negative electrode material formula. However, while improving battery performance, this design does not fully solve the problem of the utilization efficiency of the multi-layer zinc negative electrode, and lacks technical means to effectively control the electrolyte concentration, which limits the further improvement of the overall energy density of the battery and the cycle stability.

[0003] Chinese invention patent CN116759584 proposes an ultra-high specific surface area current collector of a surface-deposited oxide / carbon composite material, which greatly improves the charge and discharge performance and specific capacity of the positive electrode material and is suitable for secondary aqueous zinc-ion battery applications. However, the patent does not directly improve the dynamic management of electrolyte concentration in zinc-manganese batteries and the design of the negative electrode layered structure, which to a certain extent restricts its actual application effect in high-capacity disposable or rechargeable zinc-manganese batteries.

[0004] Although the above design improves environmental protection and some electrochemical performance by eliminating toxic heavy metals and optimizing the performance of electrode materials, it still has certain limitations, such as failure to fully utilize the negative electrode material, inability to intelligently adjust the electrolyte concentration to maintain a stable internal battery environment, and failure to activate the negative electrode layer by layer to extend the battery life. Summary of the invention

[0005] In view of the above-mentioned prior art, the technical problem to be solved by the present invention is how to improve the energy density and utilization rate of zinc-manganese batteries by designing a multi-layer negative electrode structure in combination with an intelligent electrolyte replenishment system.

[0006] To solve the above problems, the present invention provides a high-capacity zinc-manganese battery, comprising a shell, a first negative electrode is fixedly connected in the shell, a first partition is fixedly connected in the first negative electrode, a second negative electrode is fixedly connected in the first partition, a second negative electrode is fixedly connected in the second negative electrode, a third negative electrode is fixedly connected in the second partition, a positive electrode is arranged inside the third negative electrode, the top and bottom ends of the first negative electrode, the first partition, the second negative electrode, the second partition and the third negative electrode are respectively fixedly connected with an upper end cover and a lower end cover, a microcapsule is arranged between the third negative electrode and the positive electrode, the microcapsule is filled with concentrated electrolyte, the positive electrode is a tubular structure, and a plurality of fins are fixedly connected to the inner and outer ends of the tubular structure, a positive electrode connector is fixedly connected to the top of the positive electrode, and the top end of the positive electrode connector passes through the upper end cover upward and extends to the upper side of the upper end cover.

[0007] In the above-mentioned high-capacity zinc-manganese battery, the efficient utilization of zinc negative electrode materials is achieved through the multi-layer stacked negative electrode structure, and combined with the intelligent electrolyte replenishment system, the stability of the electrolyte concentration during discharge is ensured, thereby improving the energy density and total capacity of the battery. The positive electrode adopts an optimized design to increase the contact area between the active material and the electrolyte, further enhancing the battery's charge and discharge performance. At the same time, the use of pH-responsive microcapsule technology solves the problem of performance degradation caused by electrolyte dilution in traditional zinc-manganese batteries during long-term use, effectively extending the battery life.

[0008] As a further improvement of the present application, a collecting electrode is fixedly connected to the bottom end of the lower end cover, the collecting electrode passes through the bottom end of the shell and extends to the lower side of the shell, a partition is fixedly connected to the top end of the collecting electrode, the partition is made of elastic insulating material, the top end of the partition is arranged in contact with the bottom end of the positive electrode, and a buffer chamber is formed between the collecting electrode and the partition.

[0009] As a further improvement of the present application, the buffer chamber is pre-filled with an inert gas at normal pressure during manufacturing, a positive electrode sealing ring is fixedly connected between the shell and the positive electrode connector, a negative electrode sealing ring is fixedly connected between the shell and the collector, the positive electrode sealing ring and the negative electrode sealing ring are both clamped with the shell, the positive electrode sealing ring and the negative electrode sealing ring are both made of elastic insulating material, and a plurality of through holes are opened on the first negative electrode, the second negative electrode and the third negative electrode, and the plurality of through holes are evenly distributed around the axis of the shell.

[0010] As a further improvement of the present application, multiple fins are evenly distributed around the positive electrode axis, multiple circulation rings are opened on the multiple fins, and the multiple circulation rings are spaced and evenly distributed along the positive electrode axis direction. The first negative electrode, the second negative electrode and the third negative electrode are all hollow structures, and the first negative electrode, the second negative electrode and the third negative electrode are respectively fixedly connected to the upper end cover and the lower end cover with multiple upper bonding rings and multiple lower bonding rings, and the upper end cover and the lower end cover are both multi-layer structures corresponding to the first negative electrode, the second negative electrode and the third negative electrode one by one, and the positive electrode and the third negative electrode are filled with electrolyte.

[0011] As another improvement of the present application, the first negative electrode, the second negative electrode and the third negative electrode each include at least one inner zinc foil and an outer zinc active layer, the inner zinc foil is made of high-purity zinc and has a thickness in the range of 50-100 microns, and the outer zinc active layer can be obtained by coating a porous zinc powder on a conductive substrate or a composite material composed of zinc powder and a conductive material (such as carbon fiber, carbon nanotubes, graphene or PEDOT:PSS), and the particle size, morphology and ratio of the zinc powder to the conductive material can be controlled by spray deposition, electrodeposition and the like.

[0012] As another improvement supplement of the present application, both the first separator and the second separator are made of water-soluble polymer composite films containing soluble salts (such as NaCl, KCl or LiCl) to isolate the positive and negative electrodes and allow ions to pass through.

[0013] As another improved supplement to the present application, the multiple concentrated electrolytes are all concentrated potassium hydroxide electrolytes, the multiple microcapsules are all made of pH responsive materials, the pH responsive materials can be selected from polyethylene glycol-methacrylate, maleic anhydride copolymer or poly (N-isopropylacrylamide), etc., and the preparation method of the multiple microcapsules can adopt a microemulsion method, a solvent evaporation method and the like.

[0014] As another improvement of the present application, multiple upper adhesive rings and lower adhesive rings all use acid-sensitive polyelectrolytes or current-triggered degradable conductive polymers as smart adhesives. The smart adhesives can be but are not limited to polyacrylic acid (PAA), polyethyleneimine (PEI), poly(N,N-dimethylacrylamide), PEDOT:PSS, poly(3,4-ethylenedioxythiophene) (PEDOT), etc., and their properties can be adjusted by modification methods such as copolymerization and cross-linking. The shell is made of degradable or recyclable materials, such as polylactic acid (PLA) or polyethylene terephthalate glycol (PETG).

[0015] In summary, this application has the following beneficial effects:

[0016] 1. The layered stacked negative electrode structure and electrochemical performance are improved by adopting a multi-layer negative electrode, a first negative electrode, a second negative electrode and a third negative electrode design, and each negative electrode is isolated by a first separator and a second separator, so that the next layer can continue to participate in the reaction after the negative electrode material of the previous layer is consumed, thereby improving the energy density and total capacity of the battery, thereby extending the working time of the battery.

[0017] 2. Intelligent electrolyte management system, designed with pH-responsive microcapsules filled with concentrated electrolyte. When the electrolyte concentration drops during battery discharge, the microcapsules will rupture in time according to the change in pH value to release concentrated electrolyte to replenish the main area, maintain appropriate electrolyte concentration, ensure the stability and performance consistency of the battery throughout the discharge process, and thus extend the battery life.

[0018] 3. High-efficiency positive electrode design and improved utilization of active materials. The positive electrode adopts a tubular hollow structure, and multiple groups of fins are fixed at its inner and outer ends. The fins are provided with circulation rings, which significantly increase the contact area between the active material manganese dioxide and the electrolyte, improve the fluidity of the electrolyte inside the positive electrode and the electrochemical reaction efficiency, and make more full use of the electrode material.

[0019] 4. Safety protection mechanism, by setting up a buffer chamber pre-filled with inert gas and using a partition on the top of the collector, it can not only prevent short circuit but also play a buffering role when the internal pressure of the battery changes, ensuring the structural integrity of the battery. The use of a double sealing system of positive and negative sealing rings enhances the overall sealing of the battery, effectively preventing electrolyte leakage and external material intrusion, and ensuring the safe operation of the battery.

[0020] 5. Hierarchical activation mechanism and resource conservation. The upper and lower adhesive rings use acid-sensitive or current-triggered degradation smart adhesives, so that different negative electrode layers can be activated layer by layer when the previous layer is exhausted and causes local environmental changes, thereby maximizing resource utilization.

[0021] 6. Environmental sustainability: the shell is made of biodegradable or recyclable materials, such as PLA or PETG, which conforms to the concept of environmental protection and reduces the impact on the environment.

[0022] 7. Optimized electrolyte management and cycle stability. The first and second separators are made of water-soluble polymer composite films containing soluble salts, which not only isolate the positive and negative electrodes but also allow ions to pass freely, ensuring good ion conductivity. The intelligent release mechanism of pH-responsive microcapsules can effectively regulate the electrolyte concentration, reduce the battery performance degradation caused by electrolyte dilution, and further improve the battery cycle stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the overall structure diagram of this application;

[0024] Figure 2 Partial explosion for this application Figure 1 ;

[0025] Figure 3 Partial explosion for this application Figure 2 ;

[0026] Figure 4 Partial explosion for this application Figure 3 ;

[0027] Figure 5 This is the front view of the application;

[0028] Figure 6 It is the AA cross-sectional view of this application;

[0029] Figure 7 It is the BB cross-sectional view of this application;

[0030] Figure 8 This is an enlarged view of point C of this application;

[0031] Fig. 9 This is an enlarged view of point D of this application.

[0032] Description of the numbers in the figure:

[0033] 1. Shell; 2. First negative electrode; 3. First partition; 4. Second negative electrode; 5. Second partition; 6. Third negative electrode; 7. Positive electrode; 8. Upper end cover; 9. Lower end cover; 10. Microcapsule; 11. Concentrated electrolyte; 12. Fin; 13. Positive electrode connector; 14. Collector; 15. Partition; 16. Buffer chamber; 17. Positive electrode sealing ring; 18. Negative electrode sealing ring; 19. Circulation ring; 20. Upper bonding ring; 21. Lower bonding ring. DETAILED DESCRIPTION

[0034] Two implementation modes of the present application are described in detail below with reference to the accompanying drawings.

[0035] The first implementation method:

[0036] Figure 1-9 Shown is a high-capacity zinc-manganese battery, comprising a shell 1, a first negative electrode 2 is fixedly connected in the shell 1, a first separator 3 is fixedly connected in the first negative electrode 2, a second negative electrode 4 is fixedly connected in the first separator 3, a second negative electrode 4 is fixedly connected in the second negative electrode 4, a second separator 5 is fixedly connected in the second separator 5, a third negative electrode 6 is fixedly connected in the second separator 5, a positive electrode 7 is arranged on the inner side of the third negative electrode 6, an upper end cover 8 and a lower end cover 9 are fixedly connected to the top and bottom ends of the first negative electrode 2, the first separator 3, the second negative electrode 4, the second separator 5 and the third negative electrode 6 respectively, a microcapsule 10 is arranged between the third negative electrode 6 and the positive electrode 7, the microcapsule 10 is filled with a concentrated electrolyte 11, the positive electrode 7 is a tubular structure, and a plurality of fins 12 are fixedly connected to the inner and outer ends of the tubular structure, a positive electrode connector 13 is fixedly connected to the top of the positive electrode 7, and the top end of the positive electrode connector 13 passes through the upper end cover 8 upward and extends to the upper side of the upper end cover 8.

[0037] In the above-mentioned high-capacity zinc-manganese battery, the multi-layer stacked negative electrode structure is used to achieve efficient utilization of zinc negative electrode materials, and combined with the intelligent electrolyte replenishment system, the stability of the electrolyte concentration during discharge is ensured, thereby improving the energy density and total capacity of the battery. The positive electrode 7 adopts an optimized design to increase the contact area between the active material and the electrolyte, further enhancing the battery charging and discharging performance. At the same time, the pH-responsive microcapsule technology is used to solve the problem of performance degradation caused by electrolyte dilution in traditional zinc-manganese batteries during long-term use, effectively extending the battery life.

[0038] A layered stacked negative electrode structure is used to increase the battery capacity, and the battery performance is maintained by electrolyte supplementation. In the initial state, the internal structure of the battery is a multi-layer stacking design. The first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 are stacked in sequence and isolated by the first partition 3 and the second partition 5 to prevent short circuit. The positive electrode 7 is located in the innermost layer. Fins 12 are provided at the inner and outer ends of its tubular structure to increase the contact area between the active material and the electrolyte. The concentrated electrolyte 11 is pre-stored in the microcapsule 10. When the electrolyte concentration in the battery is lower than a certain threshold, when it starts working, the concentrated electrolyte 11 will be released into the main area of ​​the battery. During the discharge process, when the battery is connected After entering the circuit, the third negative electrode 6 starts an oxidation reaction, releases electrons and is converted into zinc hydroxide. At the same time, the manganese dioxide on the positive electrode 7 participates in the chemical reaction as a catalyst, accepts electrons transferred from the negative electrode and combines with hydroxide ions in the electrolyte to generate water. As the discharge process proceeds, the third negative electrode 6 is gradually consumed. At this time, the second separator 5 loses its adhesion under appropriate conditions due to the smart binder or pH response mechanism, and the second negative electrode 4 is activated to continue to provide electrical energy output. When the electrolyte concentration decreases due to the chemical reaction, the concentrated electrolyte 11 in the microcapsule 10 is released in time and replenished into the battery body to maintain a suitable electrolyte concentration and battery performance.

[0039] The first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 in the negative electrode structure are all made of high-purity zinc material, and the negative electrodes are isolated by the first separator 3 and the second separator 5. This layered design allows the next layer to continue to participate in the chemical reaction after the zinc in the previous layer is consumed, thereby achieving high capacity. The structure and function of the positive electrode 7, the positive electrode 7 adopts a tubular structure, and the interior is filled with manganese dioxide active material as the active ingredient of the positive electrode 7. Multiple groups of fins 12 are fixedly connected to the inner and outer ends of the tube wall, which increases the contact area between the active material and the electrolyte and improves the electrochemical reaction efficiency. The electrolyte replenishment system, a microcapsule 10 is arranged between the positive electrode 7 and the third negative electrode 6, and these microcapsules The capsule 10 stores concentrated electrolyte 11 such as concentrated potassium hydroxide. When working normally, as the concentration of the electrolyte decreases due to chemical reactions during the discharge process of the battery, the microcapsule 10 will release the concentrated electrolyte 11 stored inside at a specific pH value and replenish it to the battery body in time to maintain a suitable electrolyte concentration and ensure stable operation of the battery. The entire battery assembly is sealed and protected by the shell 1. The upper end cover 8 and the lower end cover 9 are respectively fixed to the top and bottom of the negative electrode to form a closed environment to ensure the safety and reliability of the battery. A positive electrode connector 13 is provided on the top of the positive electrode 7, which penetrates the upper end cover 8 upward and extends to the outside to connect to the external circuit for current transmission.

[0040] The multi-layer negative electrode design effectively improves the energy density and total capacity of the battery, making the battery have a longer working time. The intelligent electrolyte replenishment system can automatically adjust the electrolyte concentration to ensure that the battery performance remains stable during the entire discharge process, thereby extending the battery life. The tubular structure of the positive electrode 7 and the fin 12 design increase the contact area between the active material and the electrolyte, thereby improving the utilization rate of the electrode material. The layered structure and diaphragm design effectively avoid the risk of short circuit, and the concentrated electrolyte 11 encapsulated in the microcapsule 10 can be released safely and controllably, reducing the safety hazards during battery use.

[0041] The second implementation method:

[0042] Figure 1-9 As shown, a collector 14 is fixedly connected to the bottom end of the lower end cover 9, the collector 14 passes through the bottom end of the shell 1 and extends to the lower side of the shell 1, a partition 15 is fixedly connected to the top end of the collector 14, the partition 15 is made of elastic insulating material, the top end of the partition 15 is in contact with the bottom end of the positive electrode 7, and a buffer chamber 16 is formed between the collector 14 and the partition 15.

[0043] The buffer chamber 16 is pre-filled with an inert gas at normal pressure during manufacturing, a positive electrode sealing ring 17 is fixedly connected between the shell 1 and the positive electrode connector 13, a negative electrode sealing ring 18 is fixedly connected between the shell 1 and the collector 14, the positive electrode sealing ring 17 and the negative electrode sealing ring 18 are both clamped with the shell 1, and the positive electrode sealing ring 17 and the negative electrode sealing ring 18 are both made of elastic insulating material, and a plurality of through holes are opened on the first negative electrode 2, the second negative electrode 4 and the third negative electrode 6, and the plurality of through holes are evenly distributed around the axis of the shell 1.

[0044] A plurality of fins 12 are evenly distributed around the axis of the positive electrode 7, a plurality of circulation rings 19 are provided on the plurality of fins 12, and the plurality of circulation rings 19 are spaced and evenly distributed along the axis direction of the positive electrode 7, the first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 are all hollow structures, a plurality of upper adhesive rings 20 and a plurality of lower adhesive rings 21 are fixedly connected between the first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 and the upper end cover 8 and the lower end cover 9 respectively, the upper end cover 8 and the lower end cover 9 are both multilayer structures corresponding one by one to the first negative electrode 2, the second negative electrode 4 and the third negative electrode 6, and the positive electrode 7 and the third negative electrode 6 are filled with electrolyte.

[0045] The first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 each include at least one inner zinc foil and an outer zinc active layer, the inner zinc foil is made of high-purity zinc with a thickness in the range of 50-100 microns, the outer zinc active layer can be obtained by coating porous zinc powder on a conductive substrate or a composite material composed of zinc powder and a conductive material such as carbon fiber, carbon nanotubes, graphene or PEDOT:PSS, and the particle size, morphology and ratio of the zinc powder to the conductive material can be controlled by spray deposition, electrodeposition and the like.

[0046] The first separator 3 and the second separator 5 are both made of water-soluble polymer composite films containing soluble salts such as NaCl, KCl or LiCl, which are used to separate the positive and negative electrodes and allow ions to pass through.

[0047] The multiple concentrated electrolytes 11 are all concentrated potassium hydroxide electrolytes, and the multiple microcapsules 10 are all made of pH responsive materials. The pH responsive materials can be selected from polyethylene glycol-methacrylate, maleic anhydride copolymer or poly (N-isopropylacrylamide), etc. The preparation method of the multiple microcapsules 10 can adopt a microemulsion method, a solvent evaporation method and the like.

[0048] The multiple upper adhesive rings 20 and the lower adhesive rings 21 all use acid-sensitive polyelectrolytes or current-triggered degradable conductive polymers as smart adhesives. The smart adhesives can be but are not limited to polyacrylic acid (PAA), polyethyleneimine (PEI), poly(N,N-dimethylacrylamide), PEDOT:PSS, poly(3,4-ethylenedioxythiophene) (PEDOT), etc., and their properties can be adjusted by modification methods such as copolymerization and cross-linking. The shell 1 is made of degradable or recyclable materials, such as polylactic acid (PLA) or polyethylene terephthalate glycol (PETG).

[0049] Electrochemical reaction and energy output, the positive electrode 7 adopts a hollow tubular structure containing a catalyst manganese dioxide, and has a plurality of fins 12, and these fins 12 are provided with circulation rings 19, which are intended to increase the surface area of ​​the active material, improve the fluidity of the electrolyte inside the positive electrode 7, and enhance the efficiency of the electrochemical reaction. The first negative electrode 2, the second negative electrode 4 and the third negative electrode 6 are all multi-layer structures, and are all composed of an inner layer of high-purity zinc foil and an outer zinc active layer. During the battery discharge process, the zinc negative electrode is oxidized to generate electrons and is transferred to the circuit through the collector 14 to achieve electrical energy output, intelligent electrolyte management and buffer The collector 14 is connected to the lower end cover 9 at the bottom, and the top is in contact with the positive electrode 7 through the partition 15. The partition 15 is an elastic insulating material to prevent short circuit and play a buffering role. A buffer chamber 16 pre-filled with an inert gas at normal pressure is formed between the collector 14 and the partition 15 to cope with possible pressure changes and protect the integrity of the battery structure. The electrolyte is filled between the positive electrode 7 and the third negative electrode 6. At the same time, the first partition 3 and the second partition 5 use a water-soluble polymer composite film containing soluble salts, which not only isolates the positive and negative electrodes but also allows ions to pass freely for charge transfer. The electrolyte Concentration control, multiple concentrated electrolyte 11 microcapsules 10 are made of pH-responsive materials, containing concentrated potassium hydroxide electrolyte. When the pH value inside the battery changes and reaches a certain threshold, it will automatically rupture to release concentrated electrolyte 11, replenish the electrolyte diluted by discharge consumption, and maintain the concentration of effective components of the electrolyte, thereby ensuring stable battery performance. Smart adhesive and hierarchical activation mechanism, the upper adhesive ring 20 and the lower adhesive ring 21 use acid-sensitive or current-triggered degradation smart adhesives. When a certain negative electrode reacts completely, causing a local pH drop or a specific current threshold is reached, The corresponding binder loses its adhesive force, allowing the next layer of negative electrode to begin to participate in the reaction, achieving layer-by-layer activation and extending the battery life. For sealing and safety measures, the shell 1 and the positive electrode connector 13 and the collector 14 are fixed and clamped by the positive electrode sealing ring 17 and the negative electrode sealing ring 18 respectively to ensure the overall sealing and prevent electrolyte leakage. The positive electrode sealing ring 17 and the negative electrode sealing ring 18 are also made of elastic insulating materials, which enhances the safety and durability of the battery. For environmental protection and sustainability, the shell 1 is made of degradable or recyclable materials such as PLA or PETG, which is in line with environmental protection concepts.

[0050] Battery assembly and inflation. During the battery manufacturing process, the outer zinc active layer coated with porous zinc powder or the zinc negative electrode material composed of zinc powder and conductive material is first assembled according to a layered structure. The inner layer is a high-purity zinc foil, which is fixed to the upper end cover 8 and the lower end cover 9 by an upper adhesive ring 20 and a lower adhesive ring 21 using an intelligent adhesive. The partition 15 is installed on the top of the collector 14, in contact with the bottom of the positive electrode 7, and forms a buffer chamber 16. Normal pressure inert gas is pre-injected to provide internal pressure stability and safety. The electrolyte is filled between the positive electrode 7 and the third negative electrode 6, and a plurality of pH-responsive microcapsules 10 are pre-placed at appropriate positions, which are filled with concentrated potassium hydroxide electrolyte. During the battery activation and discharge process, when the battery is connected to the circuit, the first negative electrode 2 begins to react, the zinc negative electrode is oxidized to release electrons, and the electrons are transferred to the external circuit through the collector 14. At the same time, a reduction reaction occurs at the positive electrode 7. Since the positive electrode 7 adopts a tubular structure with fins 12 and a circulation ring 19, it ensures that the electrolyte is evenly distributed and can Rapidly participate in chemical reactions and improve electrochemical performance. When the third negative electrode 6 is exhausted, the local environmental acidity increases or reaches a specific current threshold, causing the smart binder to degrade or lose adhesion. At this time, the second negative electrode 4 begins to work, and so on to the first negative electrode 2. The electrolyte concentration is regulated and supplemented. During the discharge process, if the electrolyte is diluted due to chemical reactions, the pH-responsive microcapsule 10 ruptures after sensing the change in environmental pH, releasing concentrated electrolyte 11 to supplement the main electrolyte, maintaining the stability of the concentration of the electrolyte's effective ingredients, and extending the battery life. Safety protection and sealing effect, the positive electrode sealing ring 17 and the negative electrode sealing ring 18 are respectively located between the shell 1 and the positive electrode connector 13 and the collector 14, forming a good sealing effect to prevent electrolyte leakage and external material intrusion. The inert gas in the buffer chamber 16 can absorb excess gas that may be generated inside the battery. At the same time, when the pressure in the battery increases, the internal pressure of the battery is kept stable to a certain extent, thereby improving the safety of the battery.

[0051] Through layered design and intelligent activation mechanism, the battery can make full use of each layer of negative electrode material, thereby significantly improving the energy density and total capacity of the battery. The pH-responsive microcapsule 10 automatically adjusts the electrolyte concentration to ensure the performance stability of the battery during discharge, which helps to extend the battery cycle life. A double sealing system and a buffer chamber 16 design are adopted to effectively avoid safety hazards such as electrolyte leakage and short circuit. Degradable or recyclable materials are used to make the shell 1. The special structural design of the positive electrode 7 improves the utilization rate of active substances and ensures the optimization of the overall battery performance.

[0052] In view of current practical needs, the above-mentioned implementation mode adopted in this application is not limited to the scope of protection. Various changes made within the knowledge scope of technical personnel in this field without departing from the concept of this application still fall within the scope of protection of the present invention.

Claims

1. A high capacity zinc-manganese battery, characterized in that: The invention comprises a shell (1), a first negative electrode (2) being fixedly connected inside the shell (1), a first partition (3) being fixedly connected inside the first negative electrode (2), a second negative electrode (4) being fixedly connected inside the first partition (3), a second negative electrode (4) being fixedly connected inside the second negative electrode (4) being fixedly connected inside the second partition (5), a third negative electrode (6) being fixedly connected inside the second partition (5), a positive electrode (7) being arranged inside the third negative electrode (6), the first negative electrode (2), the first partition (3), the second negative electrode (4), the second partition (5) and the third negative electrode (6) being fixedly connected inside the second partition (5). The top and bottom ends of the third negative electrode (6) are respectively fixedly connected to an upper end cover (8) and a lower end cover (9); a microcapsule (10) is provided between the third negative electrode (6) and the positive electrode (7); the microcapsule (10) is filled with a concentrated electrolyte (11); the positive electrode (7) is a tubular structure, and the inner and outer ends of the tubular structure are both fixedly connected to a plurality of fins (12); the top end of the positive electrode (7) is fixedly connected to a positive electrode connector (13); the top end of the positive electrode connector (13) penetrates the upper end cover (8) upwards and extends to the upper side of the upper end cover (8); The plurality of fins (12) are evenly distributed around the axis of the positive electrode (7); the plurality of fins (12) are provided with a plurality of circulation rings (19); the plurality of circulation rings (19) are spaced and evenly distributed along the axis of the positive electrode (7); the first negative electrode (2), the second negative electrode (4) and the third negative electrode (6) are all hollow structures; the first negative electrode (2), the second negative electrode (4) and the third negative electrode (6) are respectively fixedly connected with the upper end cover (8) and the lower end cover (9) with a plurality of upper bonding rings (20) and a plurality of lower bonding rings (21); the upper end cover (8) and the lower end cover (9) are both multilayer structures corresponding to the first negative electrode (2), the second negative electrode (4) and the third negative electrode (6); and an electrolyte is filled between the positive electrode (7) and the third negative electrode (6); The first separator (3) and the second separator (5) are both made of a water-soluble polymer composite film containing soluble salts, which is used to separate the positive and negative electrodes and allow ions to pass through; The plurality of concentrated electrolytes (11) are all concentrated potassium hydroxide electrolytes, the plurality of microcapsules (10) are all made of a pH-responsive material, the pH-responsive material is selected from polyethylene glycol-methacrylate, maleic anhydride copolymer or poly(N-isopropylacrylamide), and the preparation method of the plurality of microcapsules (10) adopts a microemulsion method or a solvent evaporation method.

2. A high capacity zinc-manganese battery according to claim 1, characterized in that: A collector (14) is fixedly connected to the bottom end of the lower end cover (9), the collector (14) passes through the bottom end of the shell (1) and extends to the lower side of the shell (1), a partition (15) is fixedly connected to the top end of the collector (14), the partition (15) is made of elastic insulating material, the top end of the partition (15) is arranged in contact with the bottom end of the positive electrode (7), and a buffer chamber (16) is formed between the collector (14) and the partition (15).

3. A high capacity zinc-manganese battery according to claim 2, characterized in that: The buffer chamber (16) is pre-filled with an inert gas at normal pressure. A positive electrode sealing ring (17) is fixedly connected between the shell (1) and the positive electrode connector (13). A negative electrode sealing ring (18) is fixedly connected between the shell (1) and the collector (14). The positive electrode sealing ring (17) and the negative electrode sealing ring (18) are both clamped with the shell (1). The positive electrode sealing ring (17) and the negative electrode sealing ring (18) are both made of elastic insulating material. A plurality of through holes are formed on the first negative electrode (2), the second negative electrode (4) and the third negative electrode (6), and the plurality of through holes are evenly distributed around the axis of the shell (1).

4. A high capacity zinc-manganese battery according to claim 1, characterized in that: The first negative electrode (2), the second negative electrode (4) and the third negative electrode (6) each comprise at least one inner zinc foil and an outer zinc active layer, wherein the inner zinc foil is made of high-purity zinc and has a thickness in the range of 50-100 microns, and the outer zinc active layer is a composite material composed of zinc powder and a conductive material, wherein the particle size, morphology and ratio of the zinc powder to the conductive material are controlled by a spray deposition method or an electrodeposition method.

5. A high capacity zinc-manganese battery according to claim 1, characterized in that: The plurality of upper adhesive rings (20) and lower adhesive rings (21) all use acid-sensitive polyelectrolytes or current-triggered degradable conductive polymers as smart adhesives, wherein the smart adhesives include but are not limited to polyacrylic acid, polyethyleneimine, poly(N,N-dimethylacrylamide), PEDOT:PSS, and poly(3,4-ethylenedioxythiophene), and the shell (1) is made of degradable or recyclable materials.

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