Alkaline zinc-manganese battery and manufacturing method of diaphragm cylinder of alkaline zinc-manganese battery

Abstract

The invention discloses an alkaline zinc-manganese battery and a manufacturing method of a diaphragm cylinder of the alkaline zinc-manganese battery, and relates to the field of chemical power sources, the alkaline zinc-manganese battery comprises a shell, a plurality of positive electrode rings, a spiral cylindrical diaphragm cylinder, a current collector, a zinc paste electrolyte and a filling ring, the spiral cylindrical diaphragm cylinder is formed by winding parallelogram-shaped diaphragm paper, the sealing edge of the diaphragm paper on the outermost layer is closed up in a spiral mode, the sealing edge of the diaphragm paper on the outermost layer with an inclined angle can be tightly attached to the diaphragm paper on the inner layer, opening is not prone to occurring, and the deformation resistance is higher. The sealing ring can completely shrink the opening part of the diaphragm cylinder, so that the vibration resistance of the battery is improved; the filling ring is arranged in a space lacked by the positive ring, so that contact between zinc paste overflowing from the negative electrode and the positive electrode is effectively blocked, and risks of battery heating, liquid leakage and even failure caused by internal short circuit of the battery are avoided; the filling ring has an axial propping and supporting effect on the positive electrode ring, so that the manganese ring is prevented from floating when the battery is collided and impacted, and the internal structure of the battery is kept stable.

Description

Technical Field

[0001] The invention relates to the technical field of chemical power sources, in particular to an alkaline zinc-manganese battery and a method for manufacturing a diaphragm cylinder of the alkaline zinc-manganese battery. Background Art

[0002] Alkaline zinc-manganese batteries have the advantages of high energy efficiency, long storage time, moderate cost, reliable safety performance, and wide application range. Existing zinc-manganese batteries are still mainly cheap zinc-manganese dry batteries, and the penetration rate of alkaline zinc-manganese batteries is low. Low-cost alkaline zinc-manganese batteries are not only more in line with local consumption levels in terms of price, but also free of heavy metal elements such as mercury, more environmentally friendly, and can form stronger market penetration and competitiveness.

[0003] At present, in order to reduce the cost of alkaline zinc-manganese batteries, the amount of active material in the positive or negative electrode is reduced, and the height of the positive and negative electrodes is reduced, resulting in the lack of axial support on the inner and outer sides of the diaphragm tube at the mouth of the steel shell. When the battery is impacted by external force, the diaphragm tube is very easy to deform and the manganese ring is easy to float up. In addition, the sealing edge of the outermost diaphragm paper of the ordinary diaphragm tube is easy to turn outward and the seal is extended, and the seal cannot be completely retracted into the annular prism of the sealing ring. When the battery vibrates or falls, the zinc paste in the diaphragm tube is easy to overflow to the positive electrode, causing the battery to short-circuit and fail; and after the open diaphragm paper is rolled outward, it is easy to overlap with the glue layer of the steel shell, and the alkali solution passes over the glue layer, causing the battery to climb and leak, causing safety hazards in use, and the safety and reliability of use are not high.

[0004] Although the prior art discloses reducing the deformation degree of the diaphragm tube by adding a support member, for example, patent document with application number 202211644266.0 discloses an economical alkaline zinc-manganese cylindrical battery, in which a support member is arranged near the positive terminal of the battery, and the support member is supported on the bottom of the diaphragm tube, so that the top of the diaphragm tube is pressed against the collector to prevent leakage of the diaphragm tube due to deformation; however, the top opening of the diaphragm tube of this method still has the problem of being rolled outward and unable to be completely contracted in the sealing ring or unable to be pressed against the sealing ring, and the two layers of the diaphragm tube are relatively thin and are very easy to bend or collapse. When the battery is impacted, there is still a risk of zinc paste and electrolyte in the diaphragm tube overflowing from the opening of the diaphragm tube. Summary of the invention

[0005] The purpose of the present invention is to provide an alkaline zinc-manganese battery and a method for manufacturing a diaphragm cylinder of an alkaline zinc-manganese battery, in view of the problem that the economical alkaline zinc-manganese battery in the prior art has a problem that the diaphragm cylinder is easily deformed or the top seal is extended when vibrated or impacted by external force, resulting in leakage or short circuit of the alkaline zinc-manganese battery due to the reduction of positive and negative electrode filling materials.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] An alkaline zinc-manganese battery comprises: an outer shell, a plurality of positive electrode rings, a spiral cylindrical diaphragm cylinder, a current collector, and a zinc paste electrolyte; the plurality of positive electrode rings are axially stacked in the outer shell, and the spiral cylindrical diaphragm cylinder is placed inside the plurality of positive electrode rings; the bottom of the spiral cylindrical diaphragm cylinder abuts against the positive terminal; the top seal of the spiral cylindrical diaphragm cylinder shrinks inwardly and abuts against the sealing ring of the current collector; the spiral cylindrical diaphragm cylinder comprises three layers of diaphragm paper formed by winding a piece of diaphragm paper, the innermost sealing edge and the outermost sealing edge of the diaphragm paper are axially spiral and cross-overlapped; the outermost sealing edge of the diaphragm paper is away from the two ends of the spiral cylindrical diaphragm cylinder; the zinc paste electrolyte is filled in the spiral cylindrical diaphragm cylinder.

[0008] The alkaline zinc-manganese battery of the present invention is provided with a spiral cylindrical diaphragm tube, the bottom of which is in contact with the positive terminal, and the seal on the top is contracted and in contact with the sealing ring of the current collector. When the seal on the top is contracted by vibration or external force impact, the spiral cylindrical diaphragm tube is provided. On the one hand, the innermost and outermost sealing edges of the three-layer diaphragm paper are axially spiraled and cross-overlapped, which can enhance the side wall support strength of the diaphragm tube, and further when the external force vibrates or impacts, the probability of the diaphragm tube being flattened or deformed can be reduced, and it is not easy to open, and the anti-deformation ability is improved. On the other hand, by cooperating with the edge sealing principle of the outermost layer of diaphragm paper at both ends of the spiral cylindrical diaphragm tube, after the diaphragm tube is installed in the outer shell, the sealing edge is not close to the top or bottom of the spiral cylindrical diaphragm tube, which can prevent the sealing edge from rolling outward, so that the seal on the top of the diaphragm tube can be completely contracted and abut against the sealing ring of the collector, avoiding leakage or short circuit caused by the opening at the top of the diaphragm tube. The above two aspects are coordinated to improve the safety and reliability of the use of alkaline zinc-manganese batteries.

[0009] Preferably, in the alkaline zinc-manganese battery described in the present invention, an axially concave abutment groove is provided on one side of the sealing ring close to the spiral cylindrical diaphragm tube; the side wall of the abutment groove radially abuts against the outer side wall of the spiral cylindrical diaphragm tube; and the top wall of the abutment groove abuts against the top seal of the spiral cylindrical diaphragm tube.

[0010] As a preferred embodiment of the present invention, an abutment groove is provided on the sealing ring, and the side wall of the abutment groove radially abuts against the outer side wall of the spiral cylindrical diaphragm tube, thereby enhancing the lateral protective force on the top seal of the spiral cylindrical diaphragm tube and reducing the possibility of deformation or eversion of the top seal. Correspondingly, the top wall of the abutment groove abuts against the top seal of the spiral cylindrical diaphragm tube, thereby enhancing the axial protection of the top seal, thereby enhancing the protective effect of the top seal of the spiral cylindrical diaphragm tube in the axial and radial directions, further reducing the risk of zinc paste electrolyte leakage from the top seal of the spiral cylindrical diaphragm tube, and improving the reliability of the alkaline zinc-manganese battery.

[0011] Preferably, the alkaline zinc-manganese battery described in the present invention also includes a filling ring; a plurality of the positive electrode rings are stacked axially along the positive electrode to the negative electrode of the battery; the filling ring is arranged above the positive electrode ring close to the negative electrode of the battery; the inner side of the filling ring is hollow, so that the spiral cylindrical diaphragm tube can pass through; the upper end of the filling ring abuts against the sealing ring; the height of the filled zinc paste electrolyte is equal to the height of the positive electrode ring.

[0012] As a preferred embodiment of the present invention, by arranging the positive electrode rings to be stacked axially from the positive electrode to the negative electrode of the battery, and arranging the filling rings above the positive electrode rings close to the negative electrode of the battery, the filling height of the zinc paste electrolyte is equal to the stacking height of the positive electrode rings. On the one hand, there is no sinking section of the negative electrode active material, and all the filled zinc paste electrolyte can be utilized, thereby enhancing the utilization rate of the zinc paste electrolyte. On the other hand, the section of the spiral cylindrical diaphragm cylinder corresponding to the filling ring does not need to be filled with zinc paste electrolyte, and does not affect the stability of the battery function, thereby saving the amount of filler, reducing the cost, and improving the economic benefits of the alkaline zinc-manganese battery. In coordination, by arranging the filling rings, when the battery falls or vibrates and deforms, it can be supported on a section of the side of the spiral cylindrical diaphragm cylinder close to the top seal, directly reducing the risk of the spiral cylindrical diaphragm cylinder being flattened or radially squeezed and deformed, and effectively preventing the zinc paste overflowing from the negative electrode from contacting the positive electrode, thereby avoiding the risk of causing internal short circuit of the battery to cause battery heating, leakage, and failure, further improving the safety and reliability of the alkaline zinc-manganese battery.

[0013] Preferably, in the alkaline zinc-manganese battery of the present invention, the height H of the filling ring is 1 The relationship with the total height H of the battery is: 0.04H≤H 1 ≤0.5H.

[0014] As a preferred embodiment of the present invention, by setting the ratio of the height of the filling ring to the total height of the battery, the amount of filler not filled with zinc electrolyte can be controlled as much as possible on the basis of stably generating electrical energy, thereby reducing costs and improving economic benefits.

[0015] Preferably, in the alkaline zinc-manganese battery of the present invention, the filling ring is composed of at least one of polyimide solid foam, polyetheretherketone, nylon, polytetrafluoroethylene, and silicone resin.

[0016] As a preferred embodiment of the present invention, by setting the filling ring to at least one of the polyimide solid foam, polyetheretherketone, nylon, polytetrafluoroethylene, and silicone resin, the filling ring has a certain elastic deformation ability, enhances the anti-extrusion or deformation performance, and can reduce the weight of the battery, reduce the cost of the filling ring, and improve the economic benefits of the battery.

[0017] Preferably, in the alkaline zinc-manganese battery of the present invention, the outer side wall of the filling ring is provided with an arc-shaped groove concave inward in the radial direction.

[0018] As a preferred solution of the present invention, by setting the outer wall of the filling ring as a radially concave arc-shaped groove, an axial arch support can be formed, the axial support strength is enhanced, and a certain axial elastic deformation capacity is provided, thereby preventing the upper and lower sides of the filling ring from being squeezed and broken, thereby enhancing the protective performance of the filling ring, further reducing the risk of leakage due to damage to the filling ring, and improving the anti-leakage performance.

[0019] Preferably, in the alkaline zinc-manganese battery of the present invention, the height of the filling ring is H 1 , the height H of the arc groove 2 and H 1 The relationship is: H 2 =0.8H 1 .

[0020] As a preferred solution of the present invention, by setting a proportional relationship between the height of the arc-shaped groove and the height of the filling ring, the elastic deformation capacity of the arc-shaped groove can be further enhanced, and the anti-extrusion and anti-deformation performance of the filling ring can be enhanced.

[0021] To achieve the purpose of the present invention, the present invention provides a method for manufacturing a diaphragm cylinder of an alkaline zinc-manganese battery, comprising the following steps:

[0022] S1. Adjust the angle of the cutter to cut the diaphragm paper into an acute angle of α, a bottom length of L, and a height of H. 3 A parallelogram of

[0023] S2, the acute-angle end of the diaphragm paper is fed to the winding rod, and the winding rod is rotated to wind the diaphragm paper into a spiral cylindrical diaphragm tube, so that the diaphragm paper is three-layer diaphragm paper, the edge sealing of the innermost layer and the edge sealing of the outermost layer are axially spiral and cross-overlapped, and the edge sealing of the outermost layer is away from the two ends of the spiral cylindrical diaphragm tube;

[0024] S3, sealing the bottom of the semi-finished product produced in S2 through a bottom hot stamping process to form a spiral cylindrical diaphragm tube.

[0025] The method for making a diaphragm cylinder of an alkaline zinc-manganese battery described in the present invention, wherein the spiral is understood to be achieved through the cutting and winding process of steps S1 to S2, so that the side of the parallelogram diaphragm paper is spirally wound to form a spiral cylindrical diaphragm cylinder. The diaphragm cylinder prepared has strong axial support strength and stronger deformation resistance because the innermost and outermost sealing edges of the three-layer diaphragm paper are axially spiraled and cross-overlapped; the sealing edges of the spiral cylindrical diaphragm cylinder prepared are far away from the two ends, so that the sealing edges are not easy to turn outward or open, especially the top seal is not easy to open, which avoids the top diaphragm paper from overlapping the steel shell glue layer, thereby avoiding the alkali solution from crossing the glue layer to cause the battery to climb alkali and leak, thereby improving the reliability and safety of the prepared battery.

[0026] Preferably, in the method for manufacturing the diaphragm cylinder of the alkaline zinc-manganese battery of the present invention, the angle of the acute angle α is selected in the range of 50° to 80°; and the paper feeding direction at one end of the acute angle is perpendicular to the winding direction.

[0027] As a preferred solution of the present invention, the angle of the acute angle α is set to be in the range of 50° to 80°, and one side of the parallelogram diaphragm paper is used as an edge seal, so that the length of the edge seal matches the circumference of the diaphragm tube, and the paper feeding direction at one end of the acute angle is perpendicular to the winding direction, so that the edge seals of the innermost and outermost layers of the diaphragm paper can overlap as much as possible, thereby further improving the deformation resistance of the diaphragm tube.

[0028] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0029] 1. The spiral cylindrical diaphragm tube has stronger deformation resistance. The innermost and outermost sealing edges of the three-layer diaphragm paper are axially spiraled and cross-overlapped, which can enhance the side wall support strength of the diaphragm tube, thereby reducing the probability of the diaphragm tube being flattened or deformed when subjected to external vibration or impact. It is not easy to open, has stronger deformation resistance, and reduces the risk of leakage or short circuit.

[0030] 2. By cooperating with the edge sealing principle of the outermost layer of diaphragm paper at both ends of the spiral cylindrical diaphragm tube, after the diaphragm tube is installed in the outer shell, the sealing edge is not close to the top or bottom of the spiral cylindrical diaphragm tube, which can prevent the sealing edge from rolling outward, so that the seal on the top of the diaphragm tube can be completely contracted and abut against the sealing ring of the collector, avoiding leakage or short circuit caused by the opening at the top of the diaphragm tube. The above two aspects are coordinated to improve the safety and reliability of alkaline zinc-manganese batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic structural diagram of an alkaline zinc-manganese battery of the present invention;

[0032] Figure 2 It is a structural schematic diagram of the spiral cylindrical diaphragm tube of the present invention;

[0033] Figure 3 is a schematic axial cross-sectional view of a filling ring of the present invention;

[0034] Figure 4 is a schematic top view of a filling ring of the present invention;

[0035] Figure 5 is a schematic diagram of the three-dimensional structure of the filling ring of the present invention;

[0036] Figure 6 is an X-ray transmission view of the alkaline zinc-manganese battery according to Example 1 of the present invention;

[0037] Figure 7 is an X-ray transmission view of the alkaline zinc-manganese battery described in Comparative Example 1 of the present invention;

[0038] Figure 8 This is an X-ray projection view of the alkaline zinc-manganese battery described in Comparative Example 2 of the present invention after it falls;

[0039] Fig. 9 is an X-ray projection view of the alkaline zinc-manganese battery after falling according to Example 2 of the present invention;

[0040] Fig.10 It is a schematic diagram of the state of a common diaphragm cylinder of an alkaline zinc-manganese battery described in Comparative Example 1 of the present invention;

[0041] Fig.11 It is a schematic diagram of the diaphragm paper cutting and winding simulation state of the present invention.

[0042] 1. Outer shell; 2. Positive electrode ring; 3. Spiral cylindrical diaphragm tube; 31. Diaphragm paper; 311. Innermost edge seal; 312. Outermost edge seal; 4. Collector; 41. Sealing ring; 411. Abutment groove; 42. Collector needle; 43. Negative terminal; 5. Zinc paste electrolyte; 6. Positive terminal; 7. Filling ring; 71. Arc groove; 8. Winding rod; 100. Ordinary diaphragm tube; 101. Ordinary edge seal. DETAILED DESCRIPTION

[0043] The present invention will be described in detail below in conjunction with the accompanying drawings.

[0044] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0045] Embodiment 1:

[0046] like Figure 1As shown, this embodiment provides an alkaline zinc-manganese battery, including: an outer shell 1, multiple positive electrode rings 2, a spiral cylindrical diaphragm tube 3, a collector 4, and a zinc paste electrolyte 5; the multiple positive electrode rings 2 are axially stacked in the outer shell 1, and the spiral cylindrical diaphragm tube 3 is placed on the inner side of the multiple positive electrode rings 2; the bottom of the spiral cylindrical diaphragm tube 3 abuts against the positive terminal 6; the top seal of the spiral cylindrical diaphragm tube 3 shrinks inward and abuts against the sealing ring 41 of the collector 4; the spiral cylindrical diaphragm tube 3 includes three layers of diaphragm paper 31 formed by winding a diaphragm paper 31, the innermost sealing edge 311 and the outermost sealing edge 312 of the diaphragm paper 31 are axially spiraled and axially spiraled and cross-overlapped; the outermost sealing edge 312 is far away from the two ends of the spiral cylindrical diaphragm tube 3; the zinc paste electrolyte 5 is filled in the spiral cylindrical diaphragm tube 3.

[0047] It should be noted that the current collector 4 is understood to be the current collector 4 in a common alkaline zinc-manganese battery, for example, Figure 1 As shown, the collector 4 includes: a sealing ring 41, a collector needle 42, and a negative terminal 43; the zinc paste electrolyte 5 is understood to be the zinc paste and electrolyte material in a common alkaline zinc-manganese battery; for example, the zinc paste and electrolyte matching the positive electrode.

[0048] Specifically, refer to Figure 1 As shown, the sealing ring 41 is provided with an axially concave abutment groove 411 on one side close to the spiral cylindrical diaphragm tube 3; the side wall of the abutment groove 411 radially abuts against the outer wall of the spiral cylindrical diaphragm tube 3; the top wall of the abutment groove 411 abuts against the top seal of the spiral cylindrical diaphragm tube 3.

[0049] The spiral cylindrical diaphragm tube 3 of the present invention is understood to be made by the diaphragm tube manufacturing method provided in Example 2, referring to Figure 2 As shown, the height of the spiral cylindrical diaphragm cylinder 3 can be set to 46 mm, and the bottom of the spiral cylindrical diaphragm cylinder 3 is sealed by ironing the bottom, and the bottom abuts against the inner side of the positive terminal 6 of the battery, and can block and insulate the zinc paste electrolyte 5 in the spiral cylindrical diaphragm cylinder 3 and the external positive terminal 6 and positive electrode ring 2.

[0050] The shell of the present invention can be set as a steel cylinder; it should be noted that the top of the spiral cylindrical diaphragm cylinder 3 is understood as the end close to the negative electrode of the battery, and the bottom is understood as the end close to the positive electrode of the battery; it should be noted that Figure 2 The outermost sealing edge 312 and the innermost sealing edge 311 shown also have an intermediate layer of radial thickness. Figure 2 In order to clearly show the completed winding state of the outermost edge sealing 312 and the innermost edge sealing 311, the separator paper 31 of the middle layer is not specifically shown.

[0051] The present invention is to test the X-ray image of the battery of Example 1 after the batteries of Example 1 and Comparative Example 1 are subjected to the same conditions of drop, impact or extrusion test. Figure 6 As shown, the X-ray detection image of the battery of Comparative Example 1 is as follows Figure 7 As shown; the test results show that, without the filling ring 7, the outermost sealing edge 312 of the top seal of the spiral cylindrical diaphragm tube 3 in Example 1 forms a spiral closing, which fits more closely on the adjacent inner diaphragm paper 31; reference Fig.10 As shown, the outermost ordinary edge seal 101 of the top seal of the ordinary diaphragm tube 100 in Comparative Example 1 is open to the outside, affecting the impact resistance of the battery; and, the outer opening of the edge seal at the top of the diaphragm tube in Comparative Example 1 is very close to the side wall of the outer shell 1, and may overlap with the glue layer of the steel shell wall, increasing the risk of alkali creepage and leakage of the battery.

[0052] Comparative Analysis Figure 6 and Figure 7 After the battery described in Example 1 is subjected to external force, for example, the deformation of the spiral cylindrical diaphragm tube 3 is almost zero, while after the battery described in Comparative Example 1 is subjected to external force, the ordinary diaphragm tube 100 collapses and deforms. It can be seen that the spiral cylindrical diaphragm tube 3 of Example 1 has stronger anti-deformation performance and the risk of battery leakage or short circuit is smaller.

[0053] Comparative Example 1:

[0054] This comparative example shows an alkaline zinc-manganese battery. Compared with Example 1, the difference is that the diaphragm cylinder is made of a common diaphragm cylinder 100, and the other components are the same as those of Example 2.

[0055] Embodiment 2:

[0056] Combined with the alkaline zinc-manganese battery with a common diaphragm cylinder 100 described in Comparative Example 1, Figure 7 As shown, it is found that when the battery is impacted by external force, the positive electrode manganese ring will float. Although only the spiral hollow cylindrical diaphragm cylinder is set, the battery's anti-drop performance can be improved, but after falling, ΔOV abnormalities and manganese ring floating will occur, and the stability of the internal structure of the battery needs to be optimized. Then, the structure of the alkaline zinc-manganese battery of the present invention is further optimized through Examples 2 and 3.

[0057] Based on Example 1, in this example, reference Figure 1 As shown, a plurality of positive electrode rings 2 are axially stacked on the outside of the spiral cylindrical diaphragm tube 3 and are located inside the shell; specifically, the alkaline zinc-manganese battery also includes a filling ring 7; a plurality of positive electrode rings 2 are axially stacked from the positive electrode to the negative electrode of the battery; the filling ring 7 is arranged above the positive electrode ring 2 close to the negative electrode of the battery; the inner side of the filling ring 7 is hollow, so that the spiral cylindrical diaphragm tube 3 can pass through; the upper end of the filling ring 7 abuts against the sealing ring 41; the height of the filled zinc paste electrolyte 5 is equal to the height of the positive electrode ring 2.

[0058] The positive electrode and negative electrode described in the present invention are understood to be one end of the positive terminal 6 and one end of the negative terminal 43, respectively; it can be understood that the filling ring 7 of the present invention is arranged close to one end of the negative terminal 43, and the spiral hollow diaphragm segment in the filling ring 7 does not need to be filled with zinc paste and electrolyte, thereby reducing costs and ensuring stable use of the battery, thereby realizing the manufacture of low-cost economical alkaline zinc-manganese batteries.

[0059] It should be noted that the material of the filling ring 7 can be selected from materials with high cost performance and certain hardness. Specifically, the filling ring 7 is composed of at least one of polyimide solid foam, polyetheretherketone, nylon, polytetrafluoroethylene, and silicone resin; for example, refer to Figure 1 and Figure 3 As shown, the filling ring 7 is made of porous polyimide solid foam by integral injection molding and presents a radially centrally symmetrical structure.

[0060] In this embodiment, the collector 4 seals the open upper end of the shell, three positive electrode rings 2 overlap in the shell, and the height of the positive electrode ring 2 can be selected to be 11.0-11.5 mm; the filling ring 7 is located on the upper side of the positive electrode ring 2, the spiral cylindrical diaphragm tube 3 is located in a cavity coaxial with the shell formed by the inner side of the positive electrode ring 2 and the filling ring 7, and the negative electrode zinc paste and the electrolyte are located in the spiral cylindrical diaphragm tube 3.

[0061] The height setting of the filling ring 7 of the present invention can adjust the active material filling amount and the height of the filling ring 7 according to the performance requirements of the produced battery, so as to meet the production requirements; specifically, in this embodiment, the height H of the filling ring 7 1 The relationship with the total height H of the battery is: 0.04H≤H 1 ≤0.5H; in order to improve the anti-deformation performance of the filling ring 7, refer to Figure 1 or Figure 3 As shown, the outer wall of the filling ring 7 is provided with an arc-shaped groove 71 which is concave inward in the radial direction; for example, referring to Figure 3 , Figure 4 and Figure 5 As shown, the filling ring 7 The size is 9.15±0.02mm, The size is 13.60±0.05mm, The size selection range is: Height H of the filling ring 7 1 The relationship with the total battery height H can be preferably set to H 1 =0.2H.

[0062] Specifically, the outer wall of the filling ring 7 of the present invention is provided with an arc-shaped groove 71 which is concave inward in the radial direction. The curvature radius of the arc-shaped groove 71 provided on the side wall of the filling ring 7 is 7.0 mm, and the arc height H is 2 and filling ring 7 height H1 The relationship is H 2 =0.8H 1 Similarly, non-arc groove 71 areas are provided on the upper and lower sides of the side wall of the filling ring 7, and the height H of the non-arc groove 71 area is 3 and filling ring 7 height H 1 The relationship is: 3 =0.1H 1 .

[0063] The filling ring 7 in Embodiment 2 and Embodiment 3 can effectively reduce the number of batteries with abnormal electrical characteristics after falling. A more preferred filling ring 7 is one with an arc-shaped groove 71 on the side wall, which optimizes the anti-deformation performance and saves costs.

[0064] Combination Figure 6 , Fig. 9 The test results in Table 1 show that the spiral cylindrical diaphragm cylinder 3 has a stronger ability to resist deformation. The functions of the filling ring 7 are: first, to support and protect the spiral cylindrical diaphragm cylinder 3 to prevent the spiral cylindrical diaphragm cylinder 3 from being squeezed and deformed; second, to isolate the positive and negative electrodes, and effectively prevent the negative electrode zinc paste from overflowing to the surface of the positive electrode manganese ring after the battery is impacted; third, to tighten the positive electrode ring 2 in the axial direction to prevent the manganese ring from floating when the battery is impacted.

[0065] Comparative Example 2:

[0066] This comparative example shows an alkaline zinc-manganese battery. Compared with Example 2, the difference is that the diaphragm cylinder is made of a common diaphragm cylinder 100, and the other components are the same as those in Example 2.

[0067] Comparative Example 3:

[0068] This comparative example shows an alkaline zinc-manganese battery. Compared with Example 2, the difference is that it is made of a conventional diaphragm cylinder, and the outer side wall of the filling ring 7 is not provided with an arc-shaped groove 71. The other components are the same as those of Example 2.

[0069] Embodiment 3:

[0070] On the basis of Example 2, in this embodiment, the height of the positive electrode ring 2 is 12.5-12.9 mm, and the arrangement of other components is the same as that of Example 2.

[0071] The alkaline zinc-manganese batteries in Examples 1 to 3 and Comparative Examples 1 to 3 were tested for anti-drop performance, anti-leakage performance and discharge performance. According to the schemes described in the Examples and Comparative Examples, 50 new batteries were trial-produced and dropped from a height of 1 meter onto a cement floor, with the positive electrode, negative electrode and barrel dropped twice each. The electrical characteristic parameters of the batteries were tested before and after being placed at a constant temperature for 24 hours. The floating of the manganese ring of the battery was observed using an X-ray fluoroscopy instrument. The number of batteries with abnormal electrical characteristic parameters ΔOV and the number of batteries with floating manganese rings were counted, and the test results shown in Table 1 were obtained.

[0072] Table 1: Statistics of the number of batteries with abnormal ΔOV of electrical characteristic parameters and floating manganese ring

[0073] project Number of abnormal ΔOV batteries Number of manganese ring floating batteries Example 1 2 11 Comparative Example 2 1 0 Comparative Example 3 1 0 Example 2 0 0 Example 3 0 0 Comparative Example 1 5 16

[0074] Through the dissection of the ΔOV drop abnormal battery of Comparative Example 1 in Table 1, it was found that the negative zinc paste overflowed onto the surface of the outer shell 1 and the positive electrode ring 2, causing a micro short circuit and slight heating of the battery, resulting in abnormal electrical characteristic data after the drop.

[0075] Combined with Table 1 and Fig. 9 From the analysis shown, it can be seen that the use of the filling ring 7 can effectively reduce the number of batteries with abnormal electrical characteristics after falling. The two types of filling rings 7 have similar effects. From the perspective of cost, the filling ring 7 with an arc-shaped groove 71 on the side wall shown in Example 2 is more preferred.

[0076] contrast Fig. 9 and Figure 8 As shown, the battery structures shown in Examples 2 and 3 are regular, the manganese ring has not floated, and the diaphragm tube has no bending deformation, indicating that the combined improvement of the spiral hollow cylindrical diaphragm tube and the filling ring 7 can prevent the abnormal electrical characteristic parameters and the floating phenomenon of the manganese ring after the battery falls, thereby improving the stability of the internal structure of the battery and the reliability of the battery.

[0077] The alkaline zinc-manganese battery provided by the present invention firstly provides a diaphragm tube with stronger deformation resistance. The spiral cylindrical diaphragm tube 3 formed by winding parallelogram-shaped diaphragm paper has a spirally closed sealing edge of the outermost diaphragm paper, and the outermost diaphragm paper sealing edge with an inclined angle can be tightly attached to the inner diaphragm paper, not easy to open, and has stronger deformation resistance; secondly, the abutment groove 411 at the lower part of the sealing ring can completely shrink the diaphragm tube mouth, thereby improving the vibration resistance of the battery. When the battery is impacted by a collision, the probability of deformation and collapse of the mouth of the diaphragm tube is reduced, and the negative electrode zinc paste is prevented from overflowing and contacting the positive electrode ring to cause an internal short circuit in the battery; third, the filling ring 7 can fill the space missing from the upper positive electrode ring 2, reducing the degree of deformation of the diaphragm tube when it is impacted by a collision; at the same time, it effectively blocks the zinc paste overflowing from the negative electrode from contacting the positive electrode, avoiding the risk of internal short circuit in the battery causing battery heating, leakage, and even failure; fourth, the filling ring 7 has a certain supporting effect on the positive electrode ring 2 in the axial direction, avoiding the manganese ring from floating when the battery is impacted by a collision, and maintaining the stability of the internal structure of the battery; fifth, according to performance requirements, the height of the filling ring can be adjusted according to the filling amount of the active material, and the existing equipment and components meet the production requirements, without the need for major changes or the purchase of new equipment.

[0078] The present invention also conducted leakage resistance tests on the zinc-manganese batteries described in the above embodiments and comparative examples, and the test results are shown in Table 2. Battery leakage resistance test: Ten new batteries were tested for leakage resistance under high temperature and high humidity conditions of 91°C (≥30 days) and 60°C, RH90% (≥10 weeks).

[0079] It can be seen from the leakage resistance of Table 2 that the spiral cylindrical diaphragm tube 3 of the present invention effectively improves the leakage resistance of the battery, and the filling ring 7 is arranged in coordination, so that the alkaline zinc-manganese battery of the present invention does not leak within a specified time, greatly improving the leakage resistance of the battery and ensuring the reliability of the battery.

[0080] Table 2: Test results of battery leakage resistance according to the present invention

[0081] project 91℃ 60℃, RH90% undischarged Example 1 30 days without leakage, terminated 10 weeks without leakage, terminated Comparative Example 2 30 days without leakage, terminated In the 9th week, one of the mice leaked fluid and the procedure was terminated. Comparative Example 3 30 days without leakage, terminated 2 mice leaked fluid in the 9th week and the case was terminated Example 2 30 days without leakage, terminated 10 weeks without leakage, terminated Example 3 30 days without leakage, terminated 10 weeks without leakage, terminated Comparative Example 1 On the 28th day, 2 mice leaked fluid and the procedure was terminated. 2 mice leaked fluid in the 9th week and the case was terminated

[0082] In contrast, the conventional alkaline zinc-manganese battery's ordinary diaphragm tube 100, such as the alkaline zinc-manganese batteries described in Comparative Examples 1 to 3, all experienced leakage. Upon dissection, it was found that the diaphragm and the diaphragm paper 31 with the top seal opened overlapped the rubber layer on the inner wall of the steel shell. The electrolyte that climbed due to capillary phenomenon caused the barrier failure of the rubber layer, which led to alkali creep and leakage of the battery.

[0083] The present invention also tests the discharge performance of the alkaline zinc-manganese batteries described in the above embodiments and comparative examples. According to Embodiments 1 to 3, the alkaline zinc-manganese batteries described in Comparative Examples 1 to 3 were aged at 45° C. for 2 days, and 9 of each were taken for discharge performance testing. The discharge system was the IEC project. The test results are shown in Table 3.

[0084] From the discharge performance of the batteries in the initial stage of Examples 1 to 3 and Comparative Examples 1 to 3, it can be seen that the spiral cylindrical diaphragm cylinder 3 and the filling ring 7 have no significant effect on the battery performance when they are set alone or in combination. From Examples 2 and 3, the filling amount of the positive electrode active material increases, the height of the positive electrode increases, and the discharge performance of each system is improved. The results show that in production practice, the size of the filling ring 7 can be adjusted according to the designed battery capacity; considering the drop and leakage resistance performance, the more preferred scheme is Example 2 and Example 3, where the spiral cylindrical diaphragm cylinder 3 and the filling ring 7 are set in combination, which can obtain a low-cost alkaline zinc-manganese battery with higher reliability.

[0085] Table 3: Average results of battery discharge performance test

[0086]

[0087] From the discharge performance of the batteries in the initial stage of each embodiment and comparative example, it can be seen that the spiral cylindrical diaphragm tube 3 and the filling ring 7 are used separately or in combination, and have no obvious effect on the battery performance. From Example 2 and Example 3, it can be seen that the discharge performance of each system is improved as the filling amount of the positive electrode active material increases and the positive electrode height increases. The results show that in production practice, the size of the filling ring 7 can be adjusted according to the designed battery capacity.

[0088] Considering the drop and leakage resistance performance, the more preferred solutions are embodiment 2 and embodiment 3. The spiral cylindrical diaphragm tube 3 is used in combination with the filling ring 7 with an arc-shaped groove 71 on the side wall. The low-cost alkaline zinc-manganese battery produced has higher reliability.

[0089] Embodiment 4:

[0090] like Figure 2 and Fig. 9 As shown, this embodiment provides a method for manufacturing a diaphragm cylinder of an alkaline zinc-manganese battery, and realizes the spiral cylindrical diaphragm cylinder 3 of the alkaline zinc-manganese battery as described in Example 1, comprising the following steps:

[0091] S1, adjust the angle of the cutter to cut the diaphragm paper 31 into a parallelogram with an acute angle of α, a bottom length of L, and a height of H3;

[0092] S2. The acute-angled end of the diaphragm paper 31 is fed into the winding rod 8, and the rotating winding rod 8 winds the diaphragm paper 31 into a spiral cylindrical diaphragm tube 3, so that the diaphragm paper 31 is a three-layer diaphragm paper 31, and the innermost sealing edge 311 and the outermost sealing edge 312 of the diaphragm paper 31 are axially spiral and cross-overlapped, and the outermost sealing edge 312 is far away from the two ends of the spiral cylindrical diaphragm tube 3; S3. The semi-finished product produced by S2 is sealed with a bottom ironing process to form a spiral cylindrical diaphragm tube 3.

[0093] Specifically, Figure 2 As shown, the angle selection range of the acute angle α is 50° to 80°; the paper feeding direction at one end of the acute angle is perpendicular to the winding direction.

[0094] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. An alkaline zinc-manganese battery, characterized in that: include: A shell (1), a plurality of positive electrode rings (2), a spiral cylindrical diaphragm tube (3), a current collector (4), and a zinc paste electrolyte (5); the plurality of positive electrode rings (2) are axially stacked in the shell (1), and the spiral cylindrical diaphragm tube (3) is placed inside the plurality of positive electrode rings (2); the bottom of the spiral cylindrical diaphragm tube (3) abuts against the positive electrode terminal (6); the top seal of the spiral cylindrical diaphragm tube (3) shrinks inward and abuts against the sealing ring (41) of the current collector (4); the spiral cylindrical diaphragm tube (3) comprises three layers of diaphragm paper (31) formed by winding a sheet of diaphragm paper (31), the innermost sealing edge (311) and the outermost sealing edge (312) of the diaphragm paper (31) are axially spiral and cross-overlap; the outermost sealing edge (312) is away from the two ends of the spiral cylindrical diaphragm tube (3); the zinc paste electrolyte (5) is filled in the spiral cylindrical diaphragm tube (3).

2. The alkaline zinc-manganese battery according to claim 1, characterized in that: The sealing ring (41) is provided with an axially concave abutment groove (411) on one side close to the spiral cylindrical diaphragm tube (3); the side wall of the abutment groove (411) abuts against the outer wall of the spiral cylindrical diaphragm tube (3) in the radial direction; and the top wall of the abutment groove (411) abuts against the top seal of the spiral cylindrical diaphragm tube (3).

3. The alkaline zinc-manganese battery according to claim 1, characterized in that: It also includes a filling ring (7); a plurality of the positive electrode rings (2) are stacked axially along the positive electrode of the battery toward the negative electrode; the filling ring (7) is arranged above the positive electrode ring (2) close to the negative electrode of the battery; the inner side of the filling ring (7) is hollow, so that the spiral cylindrical diaphragm tube (3) can pass through; the upper end of the filling ring (7) abuts against the sealing ring (41); the height of the filled zinc paste electrolyte (5) is equal to the height of the positive electrode ring (2).

4. The alkaline zinc-manganese battery according to claim 3, characterized in that: The relationship between the height H1 of the filling ring (7) and the total height H of the battery is: 0.04H≤H1≤0.5H.

5. The alkaline zinc-manganese battery according to claim 3, characterized in that: The filling ring (7) is made of at least one of polyimide solid foam, polyetheretherketone, nylon, polytetrafluoroethylene, and silicone resin.

6. The alkaline zinc-manganese battery according to claim 3, characterized in that: The outer side wall of the filling ring (7) is provided with an arc-shaped groove (71) which is concave inward in the radial direction.

7. The alkaline zinc-manganese battery according to claim 6, characterized in that: The relationship between the height H2 of the arc-shaped groove (71) and the height H1 of the filling ring (7) is: H2=0.8H1.

8. A method for manufacturing a diaphragm cylinder for an alkaline zinc-manganese battery, characterized in that: The method for manufacturing the spiral cylindrical diaphragm cylinder (3) of the alkaline zinc-manganese battery according to any one of claims 1 to 7 comprises the following steps: S1, adjusting the angle of the cutter to cut the diaphragm paper (31) into a parallelogram with an acute angle of α, a base length of L, and a height of H3; S2, the acute-angled end of the diaphragm paper (31) is fed to the winding rod (8), and the winding rod (8) is rotated to wind the diaphragm paper (31) into a spiral cylindrical diaphragm tube (3), so that the diaphragm paper (31) is a three-layer diaphragm paper (31), the innermost sealing edge (311) and the outermost sealing edge (312) of the diaphragm paper (31) are axially spiral and cross-overlapped, and the outermost sealing edge (312) is away from the two ends of the spiral cylindrical diaphragm tube (3); S3, sealing the bottom of the semi-finished product produced in S2 through a bottom hot stamping process to form a spiral cylindrical diaphragm tube (3).

9. The method for manufacturing a diaphragm cylinder of an alkaline zinc-manganese battery according to claim 8, characterized in that: The acute angle α is selected in the range of 50° to 80°; the paper feeding direction at one end of the acute angle is perpendicular to the winding direction.

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