CN113131046A - Alkaline zinc-manganese button cell and preparation method thereof - Google Patents
Alkaline zinc-manganese button cell and preparation method thereof Download PDFInfo
- Publication number
- CN113131046A CN113131046A CN202110412742.5A CN202110412742A CN113131046A CN 113131046 A CN113131046 A CN 113131046A CN 202110412742 A CN202110412742 A CN 202110412742A CN 113131046 A CN113131046 A CN 113131046A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- ring
- cake
- cup
- support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention discloses an alkaline zinc-manganese button cell and a manufacturing method thereof, wherein the cell comprises a support ring comprising a vertical support body and a transverse support body, a positive electrode cake is arranged in a containing groove, the peripheral surface of the positive electrode cake is tightly attached to the inner surface of the vertical support body, the upper surface of the positive electrode cake is tightly attached to the lower surface of the transverse support body, and the bottom surface of the positive electrode cake is tightly attached to the inner surface of the bottom wall of a positive electrode cup, so that the positive electrode cake is protected in the support ring and is electrically conducted with the positive electrode cup; the outer surface of the vertical supporting body is tightly attached to the inner surface of the outer peripheral wall of the anode cup, the lower end surface of the vertical supporting body is supported on the inner surface of the bottom wall of the anode cup, and the upper surface of the horizontal supporting body is supported below the sealing ring, so that the supporting ring is supported between the anode cup and the cathode top; the support ring plays a role in protecting the positive electrode cake and supporting the negative electrode, so that the size of the seal forming of the battery is stable, and the leakage-proof performance and the safety performance of the battery are improved.
Description
Technical Field
The invention relates to the field of batteries, in particular to an alkaline zinc-manganese button battery and a preparation method thereof.
Background
Alkaline zinc-manganese button cells, also known as button cells, are flat, disk-shaped cells shaped like buttons.
For example, an alkaline button cell as shown in fig. 1 is disclosed in application publication No. CN107658396A entitled "alkaline button cell sealing ring and alkaline button cell", and application publication No. CN1941461A entitled "mercury-free button cell manufacturing process and battery".
As shown in fig. 1, an alkaline button cell of the type described above comprises a positive electrode cup 1, a positive electrode active material, a negative electrode active material, an electrolyte, a separator 4, a seal ring 5, and a negative electrode top 6.
The positive electrode cup and the negative electrode top are usually formed by punching a nickel-plated thin steel plate or a stainless steel plate, and the sealing washer is made of a high polymer material with certain elasticity, and is usually polypropylene plastic. The positive active material is a cake-shaped solid formed by pressing manganese dioxide, graphite and other substances, and is commonly called as a positive electrode cake 2; the negative active material is zinc powder 3.
The production process of the alkaline button cell comprises the following manufacturing steps:
step a: pressing the positive active material into a positive electrode cake 2, pressing the positive electrode cake 2 into the positive electrode cup 1, and paving a diaphragm 4 on the positive electrode cup;
step b: the negative electrode top 6 filled with the negative electrode active material is reversely buckled on the positive electrode cup 1, so that the positive electrode cup 1 and the negative electrode top 6 are buckled with each other through a sealing gasket.
Step c: and c, forming a sealing integer on the prepared battery prefabricated product in the step b, and winding the upper edge of the peripheral wall of the positive electrode cup 1 inwards and pressing the sealing ring 5 to insulate the positive electrode and the negative electrode and keep the battery sealed.
The alkaline button cell with the structure has a plurality of problems although the production process is simple, and the defects at least comprise the following points:
first of all. When the height of the anode cake is too low, the whole anode top can sink, which not only lowers the total height of the battery, but also affects the sealing performance of the battery.
Secondly, when the height of the positive electrode cake is higher, the positive electrode cup cannot firmly hold the negative electrode top during edge curling and sealing, and the battery is easy to leak liquid and even explode.
Thirdly, when the strength of the anode cake is not enough or the anode cake is not uniformly made, the inclination of the anode top is easily caused during the sealing and forming, and the leakage of the battery is easily caused.
Fourthly, during the storage period of the battery, the anode cake is soaked in the electrolyte for a long time, so that the strength of the anode cake is changed, the support of the cathode top is weakened, and the cathode top can slightly shift, thereby affecting the sealing performance of the battery and causing the leakage of the battery.
Fifthly, when the battery is used, the structure of the positive electrode material changes along with the consumption of the active material, and the supporting stress of the positive electrode cake on the negative electrode top changes, so that the sealing performance of the battery is affected.
Disclosure of Invention
The invention aims to provide an alkaline zinc-manganese button cell with low reject ratio and excellent leakage-proof performance and a manufacturing method for producing the alkaline zinc-manganese button cell.
The technical scheme adopted by the invention for solving the technical problems is as follows: the alkaline zinc-manganese button cell comprises a positive electrode cup, a negative electrode top, a sealing ring, zinc paste, a diaphragm, a positive electrode cake, electrolyte and a support ring;
the sealing ring is arranged at the matching part of the negative pole top and the positive pole cup, so that the negative pole top and the positive pole cup are buckled up and down to form a closed chamber;
the diaphragm is positioned on the lower side of the sealing ring, the closed chamber is separated by the diaphragm to form an upper cavity and a lower cavity, the zinc paste is positioned in the upper cavity, the support ring and the anode cake are positioned in the lower cavity, and the electrolyte is positioned in the upper cavity and the lower cavity;
the support ring comprises an annular vertical support body extending axially and a transverse support body extending inwards from the upper edge of the vertical support body along the radial direction, and the vertical support body and the transverse support body are enclosed to form an accommodating groove;
the anode cake is arranged in the accommodating groove, the peripheral surface of the anode cake is tightly attached to the inner surface of the vertical supporting body, the upper surface of the anode cake is tightly attached to the lower surface of the horizontal supporting body, and the bottom surface of the anode cake is tightly attached to the bottom wall of the anode cup, so that the anode cake is protected in the supporting ring and is electrically conducted with the anode cup;
the outer surface of the vertical supporting body is tightly attached to the inner wall of the positive electrode cup, the lower end surface of the vertical supporting body is supported on the bottom wall of the positive electrode cup, and the upper surface of the horizontal supporting body is supported below the sealing ring, so that the supporting ring is supported between the positive electrode cup and the negative electrode top.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the support ring is made of stainless steel or titanium alloy.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the surface of the stainless steel support ring is covered with a nickel plating layer, and the thickness of the nickel plating layer is 0.2-3.0 microns.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the support ring is made of polytetrafluoroethylene or nylon.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the vertical support body is provided with a gap structure, so that electrolyte flows into a capillary channel between the vertical support body and the inner wall of the positive electrode cup through the gap structure.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the horizontal support body include interior ring portion, outer loop portion and connect the connecting portion of outer loop portion and interior ring body, the thickness of connecting portion be less than interior ring portion and outer loop portion, the upper and lower surface of interior ring portion and outer loop portion all flush each other, the connecting portion on be provided with the connection interior ring portion and outer loop portion's mutual spaced strengthening rib.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the diaphragm extends to the outer edge of the transverse supporting body, and the inner edge and/or the outer edge of the upper surface of the transverse supporting body are/is bent downwards to form an arc surface.
Another protection topic of the present invention is: the manufacturing method of the alkaline zinc-manganese button cell comprises the following steps:
embedding the negative pole top in a sealing ring to form a negative pole combination body, wherein the sealing ring comprises a transverse part and a vertical part, the transverse part is supported at the bottom of a flanging of the negative pole top, and the vertical part is tightly attached to the outer periphery of the flanging of the negative pole top;
adding zinc powder and electrolyte into a groove on the back surface of the negative pole top of the negative pole assembly, so that the mixture of the zinc powder and the electrolyte is adsorbed on the negative pole assembly;
mixing manganese dioxide semiconductor, graphite and electrolyte, and then sequentially performing tabletting, granulation, sieving and cake pressing processes to prepare a prefabricated anode cake;
placing the prefabricated anode cake into the accommodating groove of the support ring, and placing the prefabricated anode cake and the prefabricated anode cake into an anode cup in a downward direction to form an anode assembly;
laying a diaphragm on the upper surface of a support ring of the positive electrode assembly and injecting electrolyte into the positive electrode assembly;
the negative pole assembly filled with the mixture of zinc powder and electrolyte is reversely buckled on the positive pole assembly paved with the diaphragm, and the negative pole top and the positive pole cup are buckled with each other through a sealing ring;
and (3) sealing and shaping the positive electrode assembly and the negative electrode assembly to form the alkaline zinc-manganese button cell, and inward winding the upper edge of the outer peripheral wall of the positive electrode cup and pressing the sealing ring to keep the cell sealed.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: the relation between the height H2 of the prefabricated positive electrode cake and the depth H1 of the accommodating groove of the support ring is as follows: h1 > H2 > 0.95H 1.
The invention adopts a further preferable technical scheme for solving the technical problems as follows: and sealant is coated at the matching part of the negative pole top and the sealing ring and the matching part of the sealing ring and the positive pole cup.
Compared with the prior art, the invention has the advantages that the lower end of the vertical supporting body of the supporting ring is supported on the bottom wall of the anode cup, the horizontal supporting body of the supporting ring is supported below the sealing ring, and the height of the supporting ring is determined, so that the situation that the cathode top is wholly sunk due to over-short anode cake can be avoided during battery assembly, and the situation that the cathode top is not firmly clamped by the turned edge due to over-high anode cake can be avoided, so that the size of seal forming is stable, the seal strength is guaranteed, the leak-proof performance and the safety performance of the battery are improved, and the reject ratio of products is reduced.
Meanwhile, in the storage and use processes of the battery, the anode cake expands or loses in the support ring, and the height of the support ring is always kept constant, so that the support structure of the anode cup and the cathode top is always kept, the strength and the stability are not influenced by the storage and use processes, the battery sealing structure is prevented from being damaged, and the stability of the sealing performance of the battery is ensured.
In addition, the support ring wraps the positive electrode cake to enable the positive electrode cake and the negative electrode cake to form a whole, so that the strength of the whole positive electrode structure is increased. And the vertical supporting body and the horizontal supporting body of the supporting ring protect the corner on the outer side of the upper part of the anode cake, so that the anode cake is effectively prevented from being damaged by external extrusion force.
Drawings
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, but those skilled in the art will appreciate that the drawings are only drawn for the purpose of illustrating the preferred embodiments and therefore should not be taken as limiting the scope of the invention. Furthermore, unless specifically stated otherwise, the drawings are merely schematic representations based on conceptual representations of elements or structures depicted and may contain exaggerated displays and are not necessarily drawn to scale.
Fig. 1 is a schematic cross-sectional view of an alkaline button cell in the background of the invention;
fig. 2 is a first schematic diagram of an alkaline zinc-manganese button cell according to a first embodiment of the present invention;
fig. 3 is a second schematic diagram of an alkaline zinc-manganese button cell according to a first embodiment of the invention;
FIG. 4 is a schematic cross-sectional view taken along line A-A of FIG. 3 according to a first embodiment of the present invention;
fig. 5 is an exploded view of an alkaline zn-mn button cell according to a first embodiment of the present invention;
FIG. 6 is a first enlarged partial view of FIG. 4 according to a first embodiment of the present invention;
FIG. 7 is a second enlarged partial schematic view of FIG. 4 according to the first embodiment of the present invention;
FIG. 8 is a perspective view of a support ring according to a first embodiment of the present invention;
fig. 9 is a schematic cross-sectional view of a positive electrode assembly according to a first embodiment of the invention;
FIG. 10 is a perspective view of a support ring according to a second embodiment of the present invention;
fig. 11 is a perspective view of a support ring according to a third embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Those skilled in the art will appreciate that the description is illustrative only, and is not to be construed as limiting the scope of the invention.
It should be noted that: like reference numerals refer to like items in the following figures, and thus, once an item is defined in one figure, it may not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that the terms "front" and "back" and the like indicate orientations and positional relationships based on orientations and positional relationships shown in the drawings or orientations and positional relationships where the products of the present invention are conventionally placed in use, and are used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements to be referred must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
The first embodiment is as follows:
as shown in fig. 1-7, the present embodiment provides an alkaline zinc-manganese button cell comprising a positive electrode cup 10, a negative electrode top 60, a sealing ring 50, a zinc paste 30, a separator 40, a positive electrode cake 20, an electrolyte and a support ring 70; the sealing ring 50 is arranged at the matching part of the negative pole top 60 and the positive pole cup 10, so that the negative pole top 60 and the positive pole cup 10 are buckled up and down to form a closed chamber; the diaphragm 40 is positioned at the lower side of the sealing ring 50, the closed chamber is separated by the diaphragm 40 to form an upper cavity A and a lower cavity B, the zinc paste 30 is positioned in the upper cavity A, the support ring 70 and the anode cake 20 are positioned in the lower cavity B, and the electrolyte is positioned in the upper cavity A and the lower cavity B.
As shown in fig. 6-9, the support ring 70 includes an annular vertical support 71 extending axially and a horizontal support 72 extending radially inward from the upper edge of the vertical support 71, the vertical support 71 and the horizontal support 72 are at right angles, the middle of the horizontal support 72 is a circular through hole, and the vertical support 71 and the horizontal support 72 enclose to form a receiving groove.
The positive electrode cake 20 is arranged in the containing groove, the outer peripheral surface of the positive electrode cake 20 is tightly attached to the inner surface 71a of the vertical supporting body 71, the upper surface of the positive electrode cake 20 is tightly attached to the lower surface 72a of the horizontal supporting body 72, and the bottom surface 20c of the positive electrode cake 20 is tightly attached to the inner surface of the bottom wall 10a of the positive electrode cup 10, so that the positive electrode cake 20 is protected in the supporting ring 70 and is electrically conducted with the positive electrode cup 10.
The outer surface 71b of the vertical support 71 is closely attached to the inner surface of the annular outer peripheral wall 10b of the positive electrode cup 10, the lower end surface 71c of the vertical support 71 is supported on the bottom wall 10a of the positive electrode cup 10, and the upper surface 72b of the horizontal support 72 is supported below the seal ring 50, so that the support ring 70 is supported between the positive electrode cup 10 and the negative electrode top 60.
In the present embodiment, the support ring 70 wraps the positive electrode cake 20 to form an integral body, so that the strength of the entire positive electrode structure is increased. And the vertical support body 71 and the horizontal support body 72 of the support ring 70 protect the corner of the outer side of the upper part of the prefabricated positive electrode cake, so that the positive electrode cake 20 is effectively prevented from being damaged by external extrusion force.
Meanwhile, the support ring 70 is supported between the positive electrode cup 10 and the negative electrode top 60, so that the support force of the negative electrode top 60 is enhanced, the negative electrode top 60 can be effectively prevented from displacement and inclination, and the sealing strength is improved.
In addition, the transverse support 72 of the support ring 70 supports the lower end of the seal ring 50, increasing the longitudinal compression of the seal ring 50, further improving the sealing performance between the positive electrode cup 10 and the negative electrode top 60.
Moreover, the bottom surface of the anode cake 20 is tightly attached to the bottom wall of the anode cup 10, the conduction between the anode cake 20 and the anode cup 10 is more direct, and the battery has small ohmic internal resistance, so the battery performance is greatly improved.
Most importantly, the height of the support ring 70 is always kept constant, so that the support structure for the positive electrode cup 10 and the negative electrode top 60 is always kept, the strength and stability of the support structure are not influenced by the positive electrode cake 20, the sealing structure of the battery is prevented from being damaged, and the stability of the sealing performance of the battery is ensured.
Alternatively, the support ring 70 is made of a metal material such as stainless steel or titanium alloy. Preferably, the circular through-hole is larger than two-thirds of the diameter of the positive electrode cake 20 so that the electrolyte between the positive electrode cup 10 and the negative electrode cap 60 can be circulated through the separator 40 on the circular through-hole.
Preferably, the inner and outer edges of the upper side of the lateral support 72 of the support ring 70 are both rounded and deburred, so that the inner and outer sides of the upper surface of the lateral support 72 are both curved downward to form a circular arc surface. In this way, the support ring 70 is prevented from puncturing the diaphragm 40 to cause an internal short circuit.
It is further preferred that the surface of the support ring 70 made of stainless steel is subjected to nickel plating for preventing the electrolyte in the battery from corroding the stainless steel support ring 70, and the thickness of the nickel plating is as thick as possible in principle, and the thickness of the nickel plating is preferably 0.2 to 3.0 micrometers, and most preferably 1 micrometer, in view of cost and corrosion resistance of the nickel plating.
Preferably, the vertical support 71 and the horizontal support 72 have substantially the same thickness, and the whole support ring 70 is made of stainless steel plate by stamping, so that the manufacturing method is convenient and simple, and the production cost is low.
It is further preferable that the thickness of the vertical supports 71 is 0.3-0.9mm, so that the vertical supports 71 have a supporting strength while occupying the internal volume of the battery as small as possible.
As an alternative, the vertical support 71 is provided with a pore structure, so that the electrolyte flows into the capillary channel between the vertical support 71 and the inner wall of the positive electrode cup 10 through the pore structure. Also because when the outer surface of the vertical support 71 abuts against the inner wall of the positive cup 10, it is difficult to avoid the presence of capillary channels between the two, even if they are of the same size as possible and the contact surface is as smooth as possible, which could affect the electrical conduction between the support ring 70 and the outer peripheral wall of the positive cup 10. By filling the electrolyte in the contact area between the support ring 70 and the positive electrode cup 10 with a porous structure, the conductivity can be improved, the internal resistance of the battery can be reduced, and the electrical performance of the battery can be improved.
As shown in fig. 7, the negative electrode top 60 used in the present embodiment is formed by stamping from a nickel-plated thin steel plate or a stainless steel plate, and includes an integrally formed intermediate body 62 and a flange 61 around the intermediate body 62. The intermediate body 62 includes a circular top wall 62a and a first annular wall 62b extending downward from the edge of the circular top wall 62a, and a groove for receiving the anode material is defined between the first annular wall 62b and the circular top wall 62 a.
As shown in fig. 7, the flange 61 includes an annular connecting wall 61b extending radially outward from a lower portion of the first annular wall 62b and a second annular wall 61a extending upward from an outer portion of the annular connecting wall 61b, with a deformation gap between the first annular wall 62b and the second annular wall 61 a. Preferably, the height of the second annular wall 61a is less than the height of the first annular wall 62b, facilitating the subsequent processing of the button cell.
The positive electrode cup 10 used in this embodiment is formed by punching a thin steel plate plated with nickel or by press-forming a carbon steel plate and then performing nickel plating. As shown in fig. 6, the positive electrode cup 10 includes a circular bottom wall 10b and an annular outer peripheral wall 10b extending upward from the periphery of the bottom wall, the circular bottom wall and the annular outer peripheral wall forming a cup-shaped structure.
Preferably, the bottom of the positive electrode cup 10 is uniformly coated with a conductive coating, and the conductive coating is formed by mixing a binder, a diluent, and ultrafine graphite particles or superconducting carbon black, graphene, and carbon nanotubes.
The sealing ring 50 used in this embodiment is an injection molded support made of a polymer material with a certain elasticity, and is usually made of polypropylene plastic. The seal ring 50 includes an annular lateral portion for mounting on the underside of the annular connecting wall 61b of the negative pole tip 60 and a vertical portion located outside the second annular wall 61a of the negative pole tip 60. The inner diameter of the vertical portion of the sealing ring 50 is slightly smaller than the outer diameter of the negative pole top 60, and the inner diameter of the vertical portion of the sealing ring 50 is generally smaller than the outer diameter of the second annular wall 61a of the negative pole top 60 by 0.05-0.1mm, so that the negative pole top 60 and the sealing ring 50 are in interference fit.
The method for manufacturing the alkaline zinc-manganese button cell by using the support ring 70 and the related accessories comprises the following steps:
firstly, preparing a negative electrode:
first, the negative electrode assembly is formed by fitting the negative electrode top 60 into the gasket 50, the horizontal portion of the gasket 50 is supported by the bottom of the flange 61 of the negative electrode top 60, and the vertical portion is in close contact with the outer peripheral portion of the flange 61 of the negative electrode top 60. The lateral portion of the seal ring 50 and the annular connecting wall 61b of the flange 61 of the negative pole top 60 are fixed by a sealant. The sealant is mainly concentrated between the upper end surface of the transverse portion and the lower end surface of the annular connecting wall 61b of the negative pole top 60, and a small amount of the sealant flows between the vertical portion of the sealing ring 50 and the second annular wall 61a of the negative pole top 60, so that the negative pole top 60 and the sealing ring 50 are bonded together more firmly.
It should be noted that the sealant is coated only on the lateral portion of the sealing ring 50 and the annular connecting wall 61b of the flange 61 of the negative electrode top 60 in operation, not on the entire contact area of the negative electrode top 60 and the sealing ring 50, because the negative electrode top 60 and the sealing ring 50 are squeezed in the process of fitting the two and the subsequent battery molding process, and the sealant flows into other contact areas along with the squeezing force, and if the position where the sealant is coated is too high or too much, the sealant may overflow.
On the basis of the previous step, the negative electrode assembly is turned over, so that the groove of the intermediate body 62 of the negative electrode top 60 faces upwards, dry zinc powder is added into the groove on the back surface of the negative electrode top 60, a proper amount of electrolyte is injected, and the electrolyte and the zinc powder are mixed to generate surface tension, so that the mixture of the zinc powder and the electrolyte, namely the zinc paste 30 is adsorbed on the negative electrode assembly.
Secondly, preparing the positive electrode:
firstly, manganese dioxide semiconductor, graphite and electrolyte are mixed according to the mass ratio of 23.5: 1.7: 1, and preparing the prefabricated anode cake by sequentially carrying out tabletting, granulating, sieving and cake pressing processes.
It should be noted that, because the subsequent prefabricated positive electrode cake will also absorb the electrolyte, and the volume of the prefabricated positive electrode cake slightly expands after absorbing the electrolyte, the volume of the prefabricated positive electrode cake is slightly smaller than the preset volume of the battery design. That is, the thickness H1 of the preformed positive electrode cake is smaller than the depth H2 of the receiving groove of the support ring 70. However, the thickness H1 of the prefabricated positive electrode cake cannot be too small in order to ensure that the expanded positive electrode cake 20 is as high as possible as the receiving groove of the support ring 70 and thus makes good contact with the bottom of the positive electrode cup 10. Therefore, the relationship between the height H2 of the prefabricated positive electrode cake and the depth H1 of the receiving groove of the support ring 70 is: h1 > H2 > 0.95H 1.
In this embodiment, the depth of the receiving groove of the support ring 70 in the LR44 battery is 2.02 mm. The depth of the receiving groove of the support ring 70 in the LR932 battery was 1.04 mm. The thickness H1 of the prefabricated positive electrode cake of the LR44 battery is 1.95 +/-0.05 mm. The prefabricated positive electrode cake of the LR932 battery had a thickness H1 of 1.0 ± 0.03 mm.
Secondly, the prefabricated positive electrode cake is placed in the accommodating groove of the support ring 70, and the assembly of the prefabricated positive electrode cake and the support ring 70 is arranged in the positive electrode cup 10 in the downward direction of the prefabricated positive electrode cake to form a positive electrode assembly.
It should be understood that the prefabricated positive electrode cake has high internal strength and low edge strength during the manufacturing process, especially the outer edges of the upper and lower surfaces and the outer edges are easy to peel and defect. The corner of the outer edge of the upper part of the positive electrode cake 20 is close to the shaping part of the seal, so that the positive electrode cake is subjected to larger radial extrusion force. The support ring 70 not only covers the peripheral side wall and the upper surface of the positive electrode cake 20, but also protects the corner of the upper outer edge of the positive electrode cake 20 in the support ring 70 by the corner formed by the vertical support 71 and the horizontal support 72, so that the positive electrode cake 20 can be prevented from being damaged in the subsequent battery sealing shaping.
Thirdly, laying the diaphragm 40 on the upper surface of the support ring 70 of the positive assembly and injecting electrolyte into the positive assembly, wherein the diaphragm 40 is erected on the upper side of the prefabricated positive electrode cake by the transverse support body 72, and an expansion gap with the height of the transverse support body 72 of the support ring 70 is formed between the upper surface of the prefabricated positive electrode cake and the lower surface of the diaphragm 40.
In this embodiment, the diaphragm 40 may be a proton exchange membrane or an acetate membrane, which is required to separate the positive electrode and the negative electrode and can absorb the electrolyte. The diameter of the diaphragm 40 is therefore at least greater than the internal diameter of the transverse support 72 of the support ring 70 and also greater than the internal diameter of the transverse portion of the sealing ring 50. So that at least a portion of the membrane 40 of the molded alkaline zinc-manganese button cell is compressed between the seal ring 50 and the support ring 70. In this embodiment, it is preferred that the separator 40 extend to the outer edge of the lateral support 72, thereby ensuring that the separator 40 effectively spaces the positive and negative electrodes.
After the prefabricated positive electrode cake further absorbs the electrolyte in the positive electrode cup 10, the volume of the prefabricated positive electrode cake expands. Because of the existence of the expansion gap, the defect that the diaphragm 40 is burst due to the expansion of the anode cake 20 is effectively avoided, and the service life of the battery is prolonged.
Thirdly, forming the battery:
first, a negative electrode assembly containing a mixture of zinc powder and an electrolyte is inverted onto a positive electrode assembly on which a separator 40 is laid, and a negative electrode cap 60 and a positive electrode cup 10 are engaged with each other through a seal ring 50.
Preferably, the upper end of the positive electrode cup 10 is in a horn shape with a large top and a small bottom, and the vertical portion of the sealing ring 50 is also in an inclined shape matching the upper end of the positive electrode cup 10, so that the negative electrode assembly can be smoothly pressed into the positive electrode cup 10.
It should be noted that, during the insertion of this negative electrode assembly, the height of insertion thereof is controlled by the mold. Because the height of the support ring 70 is fixed, the embedding depth of the negative pole assembly is controllable. After insertion, the transverse support 72 of the support ring 70 supports the negative electrode assembly, avoiding problems such as tilting and sagging of the negative electrode tip 60.
Preferably, in the present embodiment, the inner end of the lateral portion of the sealing ring 50 exceeds the inner end of the lateral support 72 of the support ring 70, so as to obtain better supporting effect. The longitudinal extrusion force of the sealing ring 50 is uniform, and the sealing performance between the sealing ring 50 and the anode cup 10 and the cathode top 60 is further improved.
Finally, after the positive electrode assembly and the negative electrode assembly are assembled, the upper end of the peripheral side wall of the positive electrode cup 10 is bent, the upper edge of the positive electrode cup 10 and the upper edge of the vertical part of the sealing ring 50 are simultaneously bent inwards, so that the sealing and shaping are completed to form the alkaline zinc-manganese button cell, and the upper edge of the peripheral side wall of the positive electrode cup 10 is inwards wound and presses the sealing ring 50 to keep the cell sealed.
To verify the leakage resistance of the alkaline zn-mn button cell prepared by the above method, a comparative test was performed in this example. Except for the existence of the support ring 70, the fittings, the anode and cathode materials and the processing modes of the comparison group and the embodiment group are all consistent, and the sealing height is properly adjusted only for the reason of the support ring 70.
4000 cells of each of the prepared comparative and example batteries were collected for leak-proof testing, and the batteries were stored in a 60 ℃ high-temperature and high-humidity cabinet with 90% humidity, and tested for leakage every week, and recorded in the following table.
From the results of the cell leakage test, the alkaline zn-mn button cell with the support ring 70 is superior to the existing cell without the support ring 70 in the high-temperature and high-humidity leakage-proof performance at 60 ℃ and 90% humidity.
Example two:
based on the same inventive concept of the first embodiment, the second embodiment provides another specific implementation of the support ring. Other technical schemes are the same as the first embodiment. Only the differences between the second embodiment and the first embodiment will be described below.
As shown in fig. 10, in the present embodiment, the support ring 70' is made of a teflon material, which has excellent chemical stability, corrosion resistance, sealability, high lubrication non-adhesiveness, electrical insulation properties, and good aging resistance, so it does not participate in the reaction inside the battery, does not cause leakage due to the introduction of impurities, and maintains its original mechanical properties even if it is left in an electrolyte environment for a long time.
In this embodiment, the support ring 70' includes an annular vertical support 71' extending axially and a horizontal support 72' extending radially inward from the upper edge of the vertical support 71', the inner and outer joints of the vertical support 71' and the horizontal support 72' are rounded, and the upper and lower edges of the inner ring of the horizontal support 72' are also rounded. The rounded corners on the upper surface of the lateral supports 72 'are intended to protect the membrane from being cut by the support ring 70' during production or use. The rounded corners on the lower surface of the transverse support 72 'provide more expansion space for the anode cake, and reduce the squeezing effect of the anode cake expansion on the support ring 70' as much as possible.
Preferably, the vertical supports 71 'have a thickness of 1-2.5mm and the transverse supports 72' have a thickness of 1-1.5 mm. The lower end of the vertical support 71' is a horizontal annular surface so that it is firmly supported on the bottom wall of the positive electrode cup.
Further preferably, the vertical supports 71 'are provided with an aperture configuration K'. After the battery is formed, the electrolyte fills the inside of the pore structure K ', and flows into the capillary channel between the vertical support 71' and the inner wall of the positive electrode cup through the pore structure K '.
It should be noted that in the present embodiment, the support ring 70 'is made of teflon, which is an insulating material, so that the outer peripheral surface of the positive electrode cake and the inner side wall of the positive electrode cup are insulated by teflon, and at this time, the electrolyte filled between the pore structure K' and the capillary channel can achieve electric conduction between the outer peripheral surface of the positive electrode cake and the inner side wall of the positive electrode cup, and at the same time, ion conduction between the outer peripheral surface of the positive electrode cake and the inner side wall of the positive electrode cup can also be achieved, thereby improving the electrical performance of the.
To verify the leakage resistance of the alkaline zn-mn button cell prepared by the above method, a comparative test was performed in this example. Except for the existence of the support ring 70', the fittings, the anode and cathode materials and the processing modes of the comparison group and the embodiment group are all consistent, and the sealing height is properly adjusted only for the reason of the support ring 70'.
4000 cells of each of the prepared comparative and example batteries were collected for leak-proof testing, and the batteries were stored in a 60 ℃ high-temperature and high-humidity cabinet with 90% humidity, and tested for leakage every week, and recorded in the following table.
From the results of the cell leakage test, the alkaline zn-mn button cell with the support ring 70 'is superior to the existing cell without the support ring 70' in the high-temperature high-humidity leakage-proof performance at 60 ℃.
EXAMPLE III
Based on the same inventive concept of the first embodiment, the third embodiment provides another specific implementation of the support ring. Other technical schemes are the same as the first embodiment. Only the differences between the third embodiment and the first embodiment will be described below.
As shown in fig. 11, in the present embodiment, the support ring 70 "is made of nylon 66, nylon 610, or the like. Because the nylon material has better processing performance, the nylon material can be formed into various special-shaped pieces by injection molding, and has short production period and high effective efficiency, thereby greatly reducing the production cost of the support ring 70'.
And the nylon material has certain elastic deformation capacity, so that in the sealing shaping process, a part of radial force can be buffered through deformation, and the influence of the sealing process on the positive electrode cake is reduced.
As shown, the support ring 70 "includes an axially extending annular vertical support 71" and a transverse support 72 "formed extending radially inward from an upper edge of the vertical support 71". Wherein the inner and outer surfaces of the vertical support 71 "are smooth toroidal surfaces and both surfaces are vertical surfaces.
As shown, the lateral support 72 "includes an inner ring portion 701", an outer ring portion 702 ", and a connecting portion 703" connecting the outer ring portion 702 "and the inner ring portion 701", the connecting portion 703 "having a smaller thickness than the inner ring portion 701" and the outer ring portion 702 ". The upper and lower surfaces of the inner ring portion 701 "and the outer ring portion 702" are flush with each other, and the lower surfaces of the inner ring portion 701 ", the outer ring portion 702", and the connecting portion 703 "are a continuous plane. Of course, in order to increase the strength, particularly the longitudinal strength, of the transverse support 72 ", the connecting portion 703" is provided with ribs 704 "that connect the inner ring portion 701" and the outer ring portion 702 "at intervals.
It should be noted that, of course, the connecting portion 703 "may be connected to the upper sections of the inner ring portion 701" and the outer ring portion 702 "so that the upper surface of the transverse support 72" is a continuous plane, and the reinforcing rib 704 "is disposed on the lower side of the connecting portion 703"; alternatively, the connection portion 703 "may be connected between the inner ring portion 701" and the outer ring portion 702 ", and the rib 704" may be provided on both upper and lower sides or on either side of the connection portion 703 ".
If the wall thickness is thicker, shrinkage is easy to occur during nylon injection molding, so that the dimensional accuracy and stability of the support ring 70' are affected, and the size change of the support ring 70' can be reduced by adopting the thin-walled connecting part 703 ' to connect the inner ring part 701 ' and the outer ring part 702 '. Meanwhile, in the process of sealing and shaping the battery, the radial acting force on the support ring 70 'and the positive electrode cake is large, and the radial buffering effect can be achieved by using a proper amount of deformation capacity of the thin-wall connecting part 703', so that the positive electrode cake is further protected from being damaged.
The alkaline zinc-manganese button cell and the manufacturing method thereof provided by the invention are described in detail, the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping understanding the invention and the core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. The alkaline zinc-manganese button cell is characterized by comprising a positive electrode cup, a negative electrode top, a sealing ring, zinc paste, a diaphragm, a positive electrode cake, electrolyte and a support ring;
the sealing ring is arranged at the matching part of the negative pole top and the positive pole cup, so that the negative pole top and the positive pole cup are buckled up and down to form a closed chamber;
the diaphragm is positioned on the lower side of the sealing ring, the closed chamber is separated by the diaphragm to form an upper cavity and a lower cavity, the zinc paste is positioned in the upper cavity, the support ring and the anode cake are positioned in the lower cavity, and the electrolyte is positioned in the upper cavity and the lower cavity;
the support ring comprises an annular vertical support body extending axially and a transverse support body extending inwards from the upper edge of the vertical support body along the radial direction, and the vertical support body and the transverse support body enclose to form an accommodating groove;
the anode cake is arranged in the accommodating groove, the peripheral surface of the anode cake is tightly attached to the inner surface of the vertical supporting body, the upper surface of the anode cake is tightly attached to the lower surface of the horizontal supporting body, and the bottom surface of the anode cake is tightly attached to the inner surface of the bottom wall of the anode cup, so that the anode cake is protected in the supporting ring and is electrically conducted with the anode cup;
the outer surface of the vertical supporting body is tightly attached to the inner surface of the peripheral wall of the positive electrode cup, the lower end surface of the vertical supporting body is supported on the inner surface of the bottom wall of the positive electrode cup, and the upper surface of the horizontal supporting body is supported below the sealing ring, so that the supporting ring is supported between the positive electrode cup and the negative electrode top.
2. The alkaline zn-mn button cell according to claim 1, wherein the support ring is made of stainless steel or titanium alloy.
3. The alkaline zinc-manganese button cell according to claim 2, characterized in that the surface of said stainless steel support ring is covered with a nickel plating layer, said nickel plating layer having a thickness of 0.2-3.0 μm.
4. The alkaline zn-mn button cell according to claim 1, wherein the support ring is made of ptfe or nylon.
5. The button cell of claim 1, wherein said vertical support is provided with a void structure, such that electrolyte flows through said void structure into a capillary channel between said vertical support and an inner wall of said positive cup.
6. The button cell of claim 4, wherein said lateral support comprises an inner ring, an outer ring, and a connecting portion connecting said outer ring and said inner ring, said connecting portion has a thickness smaller than that of said inner ring and said outer ring, the upper and lower surfaces of said inner ring and said outer ring are flush with each other, and said connecting portion is provided with spaced ribs connecting said inner ring and said outer ring.
7. The button cell of claim 1, wherein the membrane extends to the outer edge of the lateral support, and the inner edge and/or the outer edge of the upper surface of the lateral support are curved downward to form a circular arc.
8. The method for making an alkaline zinc-manganese button cell according to claims 1-7, characterized in that it comprises the following steps:
embedding the negative pole top in a sealing ring to form a negative pole combination body, wherein the sealing ring comprises a transverse part and a vertical part, the transverse part is supported at the bottom of a flanging of the negative pole top, and the vertical part is tightly attached to the outer periphery of the flanging of the negative pole top;
adding zinc powder and electrolyte into a groove on the back surface of the negative pole top of the negative pole assembly, so that the mixture of the zinc powder and the electrolyte is adsorbed on the negative pole assembly;
mixing manganese dioxide semiconductor, graphite and electrolyte, and then sequentially performing tabletting, granulation, sieving and cake pressing processes to prepare a prefabricated anode cake;
placing the prefabricated anode cake into the accommodating groove of the support ring, and placing the prefabricated anode cake and the prefabricated anode cake into an anode cup in a downward direction to form an anode assembly;
laying a diaphragm on the upper surface of a support ring of the positive electrode assembly and injecting electrolyte into the positive electrode assembly;
the negative pole assembly filled with the mixture of zinc powder and electrolyte is reversely buckled on the positive pole assembly paved with the diaphragm, and the negative pole top and the positive pole cup are buckled with each other through a sealing ring;
and (3) sealing and shaping the positive electrode assembly and the negative electrode assembly to form the alkaline zinc-manganese button cell, and inward winding the upper edge of the outer peripheral wall of the positive electrode cup and pressing the sealing ring to keep the cell sealed.
9. The method of claim 8, wherein the relationship between the height H2 of the preformed positive electrode cake and the depth H1 of the receiving groove of the support ring is: h1 > H2 > 0.95H 1.
10. The method of claim 8, wherein a sealant is applied to the joint between the top of the negative electrode and the sealing ring and the joint between the sealing ring and the positive electrode cup.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110412742.5A CN113131046A (en) | 2021-04-16 | 2021-04-16 | Alkaline zinc-manganese button cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110412742.5A CN113131046A (en) | 2021-04-16 | 2021-04-16 | Alkaline zinc-manganese button cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113131046A true CN113131046A (en) | 2021-07-16 |
Family
ID=76776937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110412742.5A Pending CN113131046A (en) | 2021-04-16 | 2021-04-16 | Alkaline zinc-manganese button cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113131046A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2381397A1 (en) * | 1977-02-22 | 1978-09-15 | Accumulateurs Fixes | Electric button cell with plastics seal - has metal spacer ring between negative terminal and seal to trap any carbonate |
| JP2006032313A (en) * | 2004-06-16 | 2006-02-02 | Hitachi Maxell Ltd | Coin cell battery |
| JP2006127949A (en) * | 2004-10-29 | 2006-05-18 | Hitachi Maxell Ltd | Coin cell |
| US20060127758A1 (en) * | 2004-12-15 | 2006-06-15 | Takeshi Shishido | Negative electrode can, alkaline cell and production method for same |
| CN202259546U (en) * | 2011-07-18 | 2012-05-30 | 宜昌力佳科技有限公司 | Button-type lithium battery with insert-type supporting ring structure |
| CN203218351U (en) * | 2013-03-28 | 2013-09-25 | 深圳市力电电池有限公司 | Button lithium battery with metal supporting ring |
| CN106684400A (en) * | 2015-11-09 | 2017-05-17 | 方定元 | Button cell |
| CN208753376U (en) * | 2018-10-10 | 2019-04-16 | 力源电池科技（深圳）有限公司 | A kind of button cell |
| CN111477773A (en) * | 2020-06-05 | 2020-07-31 | 东莞市电的电子有限公司 | Battery shell structure, miniature column type lithium battery and manufacturing method |
| CN211404532U (en) * | 2019-12-11 | 2020-09-01 | 中银（宁波）电池有限公司 | Button type lithium battery |
-
2021
- 2021-04-16 CN CN202110412742.5A patent/CN113131046A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2381397A1 (en) * | 1977-02-22 | 1978-09-15 | Accumulateurs Fixes | Electric button cell with plastics seal - has metal spacer ring between negative terminal and seal to trap any carbonate |
| JP2006032313A (en) * | 2004-06-16 | 2006-02-02 | Hitachi Maxell Ltd | Coin cell battery |
| JP2006127949A (en) * | 2004-10-29 | 2006-05-18 | Hitachi Maxell Ltd | Coin cell |
| US20060127758A1 (en) * | 2004-12-15 | 2006-06-15 | Takeshi Shishido | Negative electrode can, alkaline cell and production method for same |
| CN202259546U (en) * | 2011-07-18 | 2012-05-30 | 宜昌力佳科技有限公司 | Button-type lithium battery with insert-type supporting ring structure |
| CN203218351U (en) * | 2013-03-28 | 2013-09-25 | 深圳市力电电池有限公司 | Button lithium battery with metal supporting ring |
| CN106684400A (en) * | 2015-11-09 | 2017-05-17 | 方定元 | Button cell |
| CN208753376U (en) * | 2018-10-10 | 2019-04-16 | 力源电池科技（深圳）有限公司 | A kind of button cell |
| CN211404532U (en) * | 2019-12-11 | 2020-09-01 | 中银（宁波）电池有限公司 | Button type lithium battery |
| CN111477773A (en) * | 2020-06-05 | 2020-07-31 | 东莞市电的电子有限公司 | Battery shell structure, miniature column type lithium battery and manufacturing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5843597A (en) | Ribbed gasket for miniature galvanic cell | |
| CN100403579C (en) | Sealing cell | |
| CN207233790U (en) | The cap assembly and secondary cell of secondary cell | |
| CN108428823A (en) | Secondary cell's top cap subassembly and secondary cell | |
| CA2118866A1 (en) | Bipolar battery housing and method | |
| KR20150023437A (en) | Battery sealing member | |
| CN108832037A (en) | A kind of button cell | |
| CN210110855U (en) | Battery top cap and contain its battery | |
| KR100751310B1 (en) | Cap assembly and retangular- type secondary battery therewith | |
| US5712058A (en) | Miniature galvanic cell having optimum internal volume for the active components | |
| EP1029375B1 (en) | Indented electrode cup for a galvanic cell | |
| CN214477731U (en) | Support ring and alkaline zinc-manganese button cell | |
| US5752987A (en) | Method for producing improved electrolyte-retention bipolar cells and batteries | |
| EP1142043B1 (en) | Electrochemical cell closure | |
| CN113131046A (en) | Alkaline zinc-manganese button cell and preparation method thereof | |
| JPH0572072B2 (en) | ||
| KR100865122B1 (en) | Sealed battery | |
| US3738869A (en) | Electric cell with depolarizer compensated against current erosion effects | |
| JPH1154135A (en) | Organic electrolyte battery | |
| US20010016282A1 (en) | Gastight-sealed alkaline storage battery in the form of a button cell | |
| WO1999063605A1 (en) | Electrode cup for galvanic cell | |
| JP2000315492A (en) | Storage battery assembly | |
| JPH0325863A (en) | Internally stacked battery | |
| JPH11339818A (en) | Alkaline dry battery and pressure attaching method of its positive mix | |
| JPH03266356A (en) | Manufacture of organic electrolytic battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210716 |