Background
The cylindrical alkaline battery is easy to creep alkali and leak liquid due to the good soakage between the KOH solution and the steel cylinder and the large internal gas pressure. The currently produced circular alkaline zinc-manganese primary battery is sealed in the following way: the cathode is made of zinc paste, and a copper nail is inserted into the zinc paste to be used as a current collector. The copper nails are welded with the cathode cover and then inserted into the middle hole of the sealing ring to assemble a sealing body. Then it is put into a steel cylinder with positive and negative poles. The outer diameter of the sealing ring is matched with the inner diameter of the opening of the steel cylinder. The outer diameter of the negative cover or another metal gasket is matched with the sealed outer inner diameter of the sealing ring.
See figure 1 for the drum runner (62). Then the outer diameter of the steel cylinder is shrunk and the mouth part is bent downwards (63). When the cylinder mouth is bent downwards along the axial direction of the steel cylinder, the lower part of the sealing surface of the sealing ring props against the rolling groove (64) of the steel cylinder and can not move downwards any more, and is compressed axially. When the outer diameter of the opening of the steel cylinder is compressed, the inner part of the sealing surface of the sealing ring is propped against a negative cover or a gasket (55) shown in figure 9, and the sealing ring is also compressed in the radial direction. Therefore, the sealing ring is compressed in the axial and radial directions to seal the battery, so that the aim of preventing liquid leakage is fulfilled.
Gas is often generated inside the battery, a large amount of gas is generated in the primary battery due to corrosion of zinc, or air or K is mixed during assembly 2 CO 3 . Long battery standing time or expansion by hot air, K 2 CO 3 Decompose to release CO 2 And the gas pressure inside the battery increases for other reasons. The battery has a possibility of explosion. The solution is that when the internal pressure of the battery exceeds a certain pressure, the weak part of the sealing ring is broken and gas is generatedFrom there, the body is discharged out of the battery through the small hole of the negative cover. The internal air pressure of the battery is reduced and the battery cannot explode. We call the weak point of the sealing ring as a safety door. The thickness of the safety door can control the internal pressure of the battery. But the sealing ring safety door cannot recover after being opened so that the electro-hydraulic fluid leaks out of the safety door. The battery can no longer be used. The secondary alkaline zinc-manganese dioxide battery with the cylindrical anode in a ring shape and the cathode in a zinc paste also adopts the structure. When overcharged, O is generated 2 The internal pressure increases, the safety door opens and the battery fails.
The inside of the cylindrical cadmium-nickel and hydrogen-nickel secondary battery is in a winding type, a negative electrode lead is welded at the bottom of the steel cylinder, and a positive electrode lead is welded at the lower positive electrode cover. An explosion-proof plug is arranged between the connection of the lower positive cover and the upper positive cover. The middle of the lower positive electrode cover is provided with an air hole, when the pressure inside the battery is increased due to overcharge or self-discharge, the air passes through the air hole of the lower positive electrode cover to compress the explosion-proof plug, and the air is provided with a pore passage and is discharged out of the battery through the air hole of the upper positive electrode cover. The gas is discharged, the internal gas pressure of the battery is reduced, and the explosion-proof plug is restored to the original shape to ensure that the battery is still sealed and liquid leakage is avoided. The battery can be continuously used after being recovered. However, in the battery using the paste as the negative electrode, the current cannot be drawn from the negative electrode.
Disclosure of Invention
The invention aims to improve the sealing structure of a cylindrical primary or secondary zinc battery taking zinc paste as a cathode, and the gas generated in the process of placing or charging the battery can be recovered to be continuously used without being scrapped after being discharged under a certain pressure, so that the utilization rate and the explosion-proof capability of the battery are improved.
The technical scheme involved in the invention is as follows:
the sealing structure of the cylindrical Cd-Ni battery is improved and then used in the cylindrical battery with cathode made of calamine cream. The battery takes the zinc paste as a negative electrode, current needs to be led out by a negative electrode current collector copper nail, and the copper nail needs to be positioned in the middle of the zinc paste, so that the zinc paste has uniform reaction and high utilization rate. Thus, a copper nail (7) is welded in the middle of the lower negative electrode cover (2) (for the winding type Cd-Ni battery, the lower positive electrode cover is used, and the battery polarity with Zn paste as the negative electrode is used as the negative electrode, and the lower negative electrode cover is called). The vent hole of the lower cathode cover (2) must be moved sideways, and in order to ensure that the explosion-proof plug (3) is compressed uniformly, the vent hole of the lower cathode cover (2) is changed from one hole into two symmetrical holes, which is shown in fig. 2 (21). The upper negative electrode cover (4) is flatly placed on the edge of the lower negative electrode cover (2), as shown in fig. 2 (22), and the explosion-proof plug (3) is placed in the middle. The edge (23) of the lower negative cover (2) is bent upwards at the edge (41) of the upper negative cover (4), so that the upper negative cover and the lower negative cover are tightly connected (81) to form a negative current collector, and the negative current collector is shown in figure 8.
The assembled negative current collector is inserted into a central hole (51) of the sealing ring (5), and the upper part (72) of the copper rod of the copper nail (7) is in interference fit with the central hole (51) of the sealing ring (5). The lower negative electrode cover (2) is placed at the position (55) of the sealing ring (5) to be tightly matched to form a sealing body, and the sealing body is shown in figure 9. The sealing body is inserted into the cathode zinc paste filled in the copper cylinder, the copper nail is arranged in the middle of the zinc paste, and current flows to the zinc paste from the copper nail when the battery discharges, so that the active material zinc in the zinc paste can be fully utilized. The seal ring (5) (56) is seated on the rolling groove (64) on the steel cylinder (6), and the outer diameter of the seal ring is tightly matched with the inner diameter of the steel cylinder. The steel cylinder (6) is contracted radially and axially at the opening part (63) of the steel cylinder by sealing equipment, so that the sealing surface (52) of the sealing ring (5) is compressed radially and axially to seal the battery.
The invention is characterized in that:
a sealing structure of a cylindrical battery using paste Zn or ZnO as a cathode comprises a lower cathode cover (2), an explosion-proof plug (3), an upper cathode cover (4), a sealing ring (5), a steel cylinder (6) and a copper nail (7), wherein the lower cathode cover (2) is welded with the copper nail (7), the lower cathode cover (2) is connected with the upper cathode cover (4), the explosion-proof plug (3) is placed in the middle, the copper nail (7) is inserted into a middle hole of the sealing ring (5), the lower cathode cover (2) is fixed on the upper part of the sealing ring (5) along with the tape, the copper nail (7) is inserted into the battery cathode zinc paste (9), meanwhile, the sealing ring (5) is tightly matched with the opening part of the steel cylinder (6), and the sealing ring (5) is compressed in the radial and axial directions through a rolling groove and a curling edge on the upper part of the steel cylinder (6), so that the battery is sealed. When the internal air pressure of the over-charge or self-discharge battery is increased, the air flows out from the air vent (53) of the sealing ring and uniformly flows out through the two holes (21) of the lower negative electrode cover (2), so that the explosion-proof plug (3) is stressed, and the compressed air of the explosion-proof plug (3) overflows out of the battery through the holes (42) of the upper negative electrode cover (4). After the gas pressure in the battery is reduced, the explosion-proof plug (3) restores the original shape and presses two holes (21) of the lower cathode cover (2) to prevent the gas from overflowing. The cell is sealed against leakage and can be used continuously.
The mercury-free zinc paste has the advantages that the surface can not be amalgamated after the copper nails are inserted, the Zn is easily corroded by itself due to the dissolution of Cu, and the air pressure in the battery is increased. The surface (75) of the copper nail (7) is plated with In or Sn, the hydrogen overpotential on the In or Sn is higher, and the page 3/4 of hydrogen is not easy to generate and self-corrosion is not easy to occur. If the surface coating of the copper nail (7) is damaged, copper scraps fall into zinc paste, or copper is dissolved in electrolyte, and the corrosion of Zn is accelerated. The surface coating of the copper nail (7) must not be damaged in the whole sealing body assembling process. The upper diameter and the lower diameter of a copper rod of a copper nail sold in the market are consistent, the size of the copper rod is in interference fit with a middle hole of a sealing ring, the surface of the copper nail is easily damaged when the copper nail is inserted into the middle hole of the sealing ring, and the position really needing the interference fit is only about 5mm at the contact position of the copper nail and the sealing ring. The diameter of the upper part of the copper nail, which is 5mm, is in interference fit with the middle hole of the sealing ring, and the diameters of other parts are smaller than the diameter of the middle hole of the sealing ring, so that the surface of the copper nail is not easy to damage during assembly, and the interference fit with the sealing ring is not influenced.
The copper nail (7) is lengthened by 5mm compared with the original one. When the size of the AA type battery is increased to 35mm from 30mm, most of Zn is converted into ZnO at the later stage of battery discharge, znO is not conductive, and the internal resistance of a negative electrode is increased during charging. The length of the copper nail is increased, namely the contact surface area of the copper nail and the negative electrode is increased, and the conductivity is increased.
The copper nail welding part (71) is arc-shaped, and the molten copper welded with the lower negative electrode cover (2) flows in the concave part, so that the copper scraps after welding are reduced. The falling of these copper shavings into the cell greatly accelerates the corrosion of Zn.
The shape of the explosion-proof plug (3) is trapezoidal and elastic. The bearing pressure of the explosion-proof plug (3) can be changed by changing the thickness of the explosion-proof plug (3), and the requirement is different according to different battery conditions, and can be from 2MPa to 8MPa. The thickness of the negative electrode cover changes along with the thickness change of the explosion-proof plug, so that the upper negative electrode cover and the lower negative electrode cover are in good contact, and the outer diameter of the assembled part is tightly combined with the inner diameter of the sealing surface of the sealing ring (5). The copper nail (7) is made of brass H62-68, the surface of the copper nail is plated with In or Sn, the copper nail is In the shape of an iron nail, the diameter of the nail rod is thick at the upper part and thin at the lower part, the diameter of the upper thick part is In interference fit with the middle hole of the sealing ring (5), the copper nail platform is concave, and the welding head is In the shape of an arc. The material of the sealing ring (5) is polypropylene or nylon 66, the outer diameter of the sealing surface of the sealing ring (5) is closely matched with the inner diameter of the opening of the steel cylinder (6), the inner diameter of the sealing surface is closely matched with the outer diameter of the negative electrode collector, 2-3 air holes are formed, and the copper nails (7) in the middle hole of the sealing ring (5) are matched in a sufficient mode. The steel cylinder (6) is made of 08F carbon steel plated with Ni, the thickness of the Ni plated layer is 2-4 microns on the outer layer, 1-3 microns on the inner wall, the wall thickness of the steel cylinder is 0.2-0.35 mm, and the inner diameter of the opening of the steel cylinder is tightly combined with the outer diameter of the sealing surface of the sealing ring (5). The sealing surface of the sealing ring (5) is reduced by hand pressure to 15-40% and axially compressed to 20-50% through rolling groove and edge on the steel cylinder.
The structure can be used not only for secondary zinc batteries, but also for primary alkaline zinc batteries. Primary alkaline Zn-MnO 2 The sealing ring used in the original battery sealing structure is difficult to control due to the thickness of the safety valve, the price of the plastic forming mould is higher, and the sealing ring is installedThe sealing ring safety valve is easy to damage and fail in the process of matching and is difficult to check. The brand reputation is influenced because of the liquid leakage that breaks of safety valve in the product sales process. The sealing structure of the invention is thick and cannot crack or damage the explosion-proof plug (3) when being assembled. In case of increasing gas in the battery, the explosion-proof plug (3) can play an explosion-proof role. Gas escape from the batteryAnd then the explosion-proof plug is recovered, and the battery can still be used and cannot be scrapped.
Zn-Ni、Zn-MnO 2 The secondary battery is difficult to control during charging without overcharging. Large amount of O generated inside the battery when overcharged 2 The negative electrode has too late to consume O in combination 2 The internal gas pressure of the battery is very high, and the battery can be continuously used without leakage after the gas is overflowed by adopting the sealing structure of the invention, so that the loss of the secondary battery is greatly reduced.
Drawings
FIG. 1 is a longitudinal sectional view of a Zn-Ni primary battery fabricated using the sealing structure of the present invention.
In the figure, 2 a lower cathode cover, 3 an explosion-proof plug, 4 an upper cathode cover, 5 sealing rings, 6 steel cylinders, 7 copper nails, 9 cathode calamine cream, 10 diaphragm pipes and 11 anode rings.
Fig. 2-7 are the shape diagrams of the components used in the cylindrical press ring type battery, fig. 7 copper nail, fig. 2 lower negative electrode cover, fig. 3 explosion-proof plug, fig. 4 upper negative electrode cover, fig. 5 sealing ring, fig. 6 steel cylinder. Wherein the size is zero 4/4 inch of AA size cylindrical battery.
Fig. 8 is a cross-sectional view of the negative electrode current collector with 2 lower negative electrode cap, 3 explosion proof plug, 4 upper negative electrode cap, 7 copper nail.
Fig. 9 is a cross-sectional view of the seal, 2 lower negative cover, 3 explosion proof plug, 4 upper negative cover, 5 sealing ring, 7 copper nail.