CN111430594A - High-temperature-resistant button battery and manufacturing process thereof - Google Patents
High-temperature-resistant button battery and manufacturing process thereof Download PDFInfo
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- CN111430594A CN111430594A CN202010253162.1A CN202010253162A CN111430594A CN 111430594 A CN111430594 A CN 111430594A CN 202010253162 A CN202010253162 A CN 202010253162A CN 111430594 A CN111430594 A CN 111430594A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 49
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 49
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 41
- 238000007789 sealing Methods 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 34
- 238000003825 pressing Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007723 die pressing method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 101150006573 PAN1 gene Proteins 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-temperature-resistant button battery and a manufacturing process thereof. The manufacturing process comprises the following steps: 1. preparing a bottom shell, an upper cover, an inner core and a polytetrafluoroethylene material; 2. molding the polytetrafluoroethylene material to form a sealing ring by a molding process, and embedding the upper cover in the sealing ring during molding; 3. heating the preformed product to a temperature above the melting point, and sintering; 4. reducing the sintering temperature to room temperature; 5. and (3) arranging the battery core, the sealing ring and the upper cover into the bottom shell, pressing the battery tab on the inner core together with the upper cover and the bottom shell, turning the periphery of the bottom shell inwards to form a roll pressing edge, and pressing the sealing ring through the roll pressing edge.
Description
Technical Field
The invention discloses a lithium-manganese battery, in particular to a high-temperature-resistant button battery and a manufacturing process thereof.
Background
The tire pressure monitoring system is called as TPMS for short, and is an abbreviation of tire pressure monitoring system, which can automatically monitor various conditions of a tire in real time by recording the rotating speed of the tire or an electronic sensor installed in the tire, and can provide effective safety guarantee for driving, wherein tire modules of the TPMS comprise components such as an MEMS pressure sensor, a temperature sensor, a voltage sensor, an accelerometer, a microcontroller, an RF circuit, an antenna, an L F interface, an oscillator and a battery.
Button cells, also known as button cells, are generally larger in diameter and thinner in thickness (compared to cylindrical cells such as AA 5 batteries in the market). The button cell is classified from the appearance, and the same corresponding cell is classified into a cylindrical cell, a square cell and a special-shaped cell.
Conventional button cells are mostly disposable cells, have limited electric quantity, need to be replaced after being used for a certain time, are time-consuming and labor-consuming, and are not environment-friendly. At present, button type lithium manganese batteries exist, but the conventional button type lithium manganese batteries are structurally characterized in that insulation treatment is carried out between a positive electrode and a negative electrode through a layer of insulation material, usually an insulation film or an insulation sleeve, the insulation material can generate melting or softening phenomena under a high-temperature condition, battery electrolyte can generate vaporization phenomena under the high-temperature condition, and electrolyte steam can leak from the softened or melted sealing part, so that the battery weightlessness and performance reduction are caused.
Disclosure of Invention
Aiming at the phenomenon that the button type lithium-manganese battery in the prior art can generate battery weight loss in a high-temperature environment, the invention provides the high-temperature resistant button battery and the manufacturing process thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the utility model provides a high temperature resistant button cell, the battery includes drain pan, upper cover, inner core and sealing washer, and upper cover and drain pan are mutually supported the installation and are in the same place, form the shell, and the inner core is installed in the shell, and the anodal utmost point ear and the negative pole utmost point ear of inner core are connected with upper cover and drain pan electricity respectively, and the upper cover inlays with the sealing washer and is in the same place, and the sealing washer adopts the polytetrafluoroethylene material to make.
A manufacturing process of the high-temperature-resistant button battery comprises the following steps:
step S1, preparing materials: preparing a bottom shell, an upper cover, an inner core and a polytetrafluoroethylene material;
step S2, molding: molding the polytetrafluoroethylene material to form a sealing ring by a molding process, and embedding the upper cover in the sealing ring during molding;
step S3, sintering: heating the preformed product to a temperature above the melting point, and sintering;
step S4, cooling: reducing the sintering temperature to room temperature;
step S5, rolling: the battery cell, the sealing ring and the upper cover are arranged in the bottom shell, the battery cell is communicated with the upper cover and the bottom shell through extrusion, the periphery of the bottom shell is turned inwards to form a roll pressing edge, and the sealing ring is pressed through the roll pressing edge.
The technical scheme adopted by the invention for solving the technical problem further comprises the following steps:
the positive electrode lug and the negative electrode lug are respectively connected with the shell in a pressing and conductive mode.
The periphery of the upper cover is turned outwards to form a flange, and the flange is embedded in the sealing ring.
And the periphery of the opening of the bottom shell is provided with a roller pressing edge which is turned inwards, and the roller pressing edge is turned inwards and downwards to press the sealing ring.
The polytetrafluoroethylene material is polytetrafluoroethylene powder with the particle size of 20-500 microns, and the polytetrafluoroethylene powder is sieved by a screen with 8-20 meshes before use.
The step S2 includes the following sub-steps:
step S2-1, mixing materials: mixing polytetrafluoroethylene powder with other additives, wherein the weight ratio of the polytetrafluoroethylene powder to the other additives is 100: 18-25, mixing materials by using a container rotary mixer, wherein the rotating speed of the container is about 15-20 rpm, and the mixing time is 10-20 min;
step S2-2, preforming: and uniformly adding the mixed polytetrafluoroethylene powder into a mold, pressing the mixed polytetrafluoroethylene powder into a compact preformed product at normal temperature, placing an upper cover in the mold according to a preset shape during preforming, placing the polytetrafluoroethylene PTFE powder into the mold, and performing mold pressing, wherein the preforming pressure adopted during mold pressing is 17-35 MPa, and the pressure is maintained for 10-15 minutes.
And S3, wherein the temperature rise speed is 80-120 ℃/h during sintering, the suspension method sintering or the dispersion method sintering is adopted during sintering, the polytetrafluoroethylene suspension method resin sintering temperature is 370-380 ℃, the dispersion method resin sintering temperature is 360-370 ℃, and when the temperature rise reaches the set temperature, the temperature is kept for 45-75 minutes.
The temperature is reduced at a low speed of 15-25 ℃/hour.
The invention has the beneficial effects that: according to the invention, polytetrafluoroethylene is used as a base material, and the lithium manganese battery insulating layer is prepared by matching a die pressing and high-temperature sintering process, so that the high-temperature resistance of the lithium manganese battery insulating layer can be greatly improved, and the weight loss condition of the button type lithium manganese battery under the high-temperature condition can be effectively prevented.
The invention will be further described with reference to the accompanying drawings and specific embodiments.
Drawings
Fig. 1 is a schematic perspective view of a button-type lithium manganese dioxide battery of the present invention.
Fig. 2 is a structural schematic diagram of the button type lithium manganese battery according to the present invention in an exploded state.
Fig. 3 is a schematic cross-sectional structure diagram of the button-type lithium manganese dioxide battery of the present invention.
In the figure, 1-a bottom shell, 2-an upper cover, 3-an inner core, 4-a sealing ring, 5-a flanging and 6-a roller edge pressing are carried out.
Detailed Description
The present embodiment is a preferred embodiment of the present invention, and other principles and basic structures that are the same as or similar to the present embodiment are within the scope of the present invention.
The invention protects a high-temperature-resistant button battery, which mainly comprises a bottom shell 1, an upper cover 2, an inner core 3 and a sealing ring 4, wherein the upper cover 2 and the bottom shell 1 are mutually matched and installed together to form a shell of the high-temperature-resistant button battery, the inner core 3 is installed in the shell, two tabs of the inner core 3 are respectively electrically connected with the upper cover 2 and the bottom shell 1, the upper cover 2 and the sealing ring 4 are embedded together, the sealing ring 4 is made of polytetrafluoroethylene materials, and the bottom shell 1 and the upper cover 2 can be insulated and sealed through the sealing ring 4.
In this embodiment, the inner core 3 may be a winding type inner core (core for short) or a laminated type inner core, the inner core structure is the same as that of a conventional lithium manganese battery inner core, that is, a positive electrode plate and a negative electrode plate are stacked, an insulating film is disposed between the positive electrode plate and the negative electrode plate, and then the winding type inner core is formed by winding the positive electrode plate and the negative electrode plate together, and the winding type inner core is stacked in multiple layers, that is, the laminated type inner core is formed, a positive electrode tab is connected to the positive electrode plate of the inner core 3, a negative electrode tab is connected to the negative electrode plate of the inner core 3, and the positive electrode tab and the negative electrode tab are respectively connected to the bottom case 1 and the upper cover 2.
In this embodiment, anodal utmost point ear and negative pole utmost point ear are connected with the shell through the electrically conductive mode of pressfitting respectively, are about to anodal utmost point ear and negative pole utmost point ear and paste the dress on drain pan 1 and upper cover 2 through pressure pressfitting respectively, realize electrically conductive effect through the contact. In this embodiment, the positive electrode tab and the negative electrode tab are respectively attached to the bottoms of the bottom case 1 and the upper cover 2, and may be connected to the side surfaces of the bottom case 1 and the upper cover 2, or other positions during specific implementation.
In this embodiment, the sealing ring 4 is made of teflon, and during processing, teflon powder is firstly subjected to compression molding and then subjected to high-temperature sintering (the high temperature in the present invention means a temperature higher than 350 ℃), the peripheral edge of the upper cover 2 is turned over outwards to form a flange 5, and the flange 5 is embedded in the sealing ring 4, so that the upper cover 2 cannot be separated from the sealing ring 4, and the structure of the sealing ring is more stable.
In the embodiment, the bottom shell 1 is in a cylindrical shape with one sealed end and one open end, the upper cover 2 is installed at one open end of the bottom shell 1, in the embodiment, the rolling edge 6 which is turned inwards is arranged at the periphery of the open end of the bottom shell 1, the rolling edge 6 is turned inwards and downwards (the lower part in the invention refers to the lower part when the battery is normally placed and is the same as the display direction in the attached drawing), the rolling edge 6 presses the sealing ring 4, and the sealing ring 4 together with the upper cover 2 is fixedly installed with the bottom shell 1, so that the sealing and fixing of the battery are realized.
The invention also discloses a manufacturing process of the button lithium manganese battery, which mainly comprises the following steps:
step S1, preparing materials: preparing a bottom shell 1, an upper cover 2, an inner core 3 and a polytetrafluoroethylene material (in this embodiment, the polytetrafluoroethylene material is polytetrafluoroethylene powder, preferably soft fine powder with a particle size of 20-500 microns), in this embodiment, the bottom shell 1 and the upper cover 2 can be processed by a conventional hardware processing method, such as: the manufacturing method comprises the following steps of stamping, CNC (computer numerical control) processing, metal stretching and the like, wherein the bottom shell 1 and the upper cover 2 are processed according to required overall dimensions, the bottom shell 1 is processed into a cylinder with one sealed end and one open end, the inner core 3 is processed into a wound inner core (a winding core for short) or a laminated inner core according to a conventional lithium manganese battery processing technology, and polytetrafluoroethylene powder needs to be sieved by a screen with 8-20 meshes before use so as to prevent the occurrence of lump materials and influence the use effect of a final product;
step S2, molding: the polytetrafluoroethylene material is molded to form the sealing ring 4 through a molding process, and the upper cover 2 is embedded in the sealing ring 4 during molding, wherein in the embodiment, the molding process comprises the following substeps:
step S2-1, mixing materials: mixing polytetrafluoroethylene powder with other additives, wherein the weight ratio of the polytetrafluoroethylene powder to the other additives is 100: 18-25, in this embodiment, the other assistant can be extrusion assistant (in this embodiment, the extrusion assistant can be paraffin oil or ethylene dichloride). The mixing of the polytetrafluoroethylene powder and the extrusion aid is carried out in a closed metal tank or a glass bottle, the charging amount in the container is limited below 1/2 of the volume of the container for uniform mixing, and when the extrusion aid is poured into the container, the extrusion aid cannot be poured on the inner wall of the container so as to avoid influencing the proportioning amount. In the embodiment, a container rotary mixer is used for mixing, the rotating speed of the container is about 15-20 rpm, and the mixing time is 10-20 min.
Step S2-2, preforming: uniformly adding the mixed polytetrafluoroethylene PTFE powder (together with other additives) into a die, and pressing at normal temperature to obtain a compact preformed product (namely a blank); in the embodiment, during preforming, the upper cover 2 is placed in a mold according to a preset shape, then polytetrafluoroethylene PTFE powder is placed in the mold, mold pressing is carried out, the preforming pressure adopted during mold pressing is 17-35 MPa, pressure is kept for 10-15 minutes, during pressing, air bleeding processing is carried out every 60-90 seconds, and air in gaps between the polytetrafluoroethylene PTFE powder is exhausted.
The seal ring 4 is manufactured by adopting a mould pressing method, and the advantages are obvious: the method has the advantages of small loss of raw materials, stable deformation performance, lower manufacturing cost of a forming die, good reusability, high production efficiency, realization of automatic production and the like.
In the present embodiment, attention should be paid to the influence of the compression ratio (generally, 4 to 6% for PTFE) and the molding shrinkage ratio (generally, 2.6 to 4.5% for PTFE) on the product during the molding of PTFE.
Step S3, sintering: the preformed product is heated to a temperature above the melting point for sintering, the temperature rise speed during sintering can be 80-120 ℃/h, in the embodiment, suspension sintering or dispersion sintering can be adopted during sintering, the resin sintering temperature of the polytetrafluoroethylene suspension method is higher and ranges from 370 ℃ to 380 ℃, the resin sintering temperature of the dispersion method is lower and ranges from 360 ℃ to 370 ℃, the sintering temperature is high, the shrinkage rate and the porosity are increased, and the sintering time is properly controlled. In the embodiment, when the temperature rises to the set temperature, the temperature is kept for 45-75 minutes;
step S4, cooling: cooling from the sintering temperature to room temperature, in this embodiment, slow cooling is adopted at a speed of 15-25 ℃/hour;
step S5, rolling: the battery core 3, the sealing ring 4 and the upper cover 2 are arranged in the bottom shell 1, a battery tab on the inner core is attached to the upper cover 2 and the bottom shell 1 by adopting a pressing process so as to be electrically connected, the periphery of the bottom shell 1 is turned inwards by a roller press machine to form a rolling edge 6, and the sealing ring 4 is pressed by the rolling edge 6, so that the sealing and the insulation between the upper cover 2 and the bottom shell 1 are realized.
According to the invention, polytetrafluoroethylene is used as a base material, and the lithium manganese battery insulating layer is prepared by matching a die pressing and high-temperature sintering process, so that the high-temperature resistance of the lithium manganese battery insulating layer can be greatly improved, and the weight loss condition of the button type lithium manganese battery under the high-temperature condition can be effectively prevented.
Claims (10)
1. The utility model provides a high temperature resistant button cell which characterized by: the battery comprises a bottom shell, an upper cover, an inner core and a sealing ring, wherein the upper cover and the bottom shell are matched and mounted together to form a shell, the inner core is mounted in the shell, a positive electrode lug and a negative electrode lug of the inner core are respectively electrically connected with the upper cover and the bottom shell, the upper cover and the sealing ring are embedded together, and the sealing ring is made of polytetrafluoroethylene.
2. The button cell of claim 1, wherein: the positive electrode lug and the negative electrode lug are respectively connected with the shell in a pressing and conductive mode.
3. The button cell of claim 1, wherein: and the positive pole lug and the negative pole lug are respectively pressed and attached to the bottom of the bottom shell and the bottom of the upper cover.
4. The button cell of claim 1, wherein: the periphery of the upper cover is turned outwards to form a flange, and the flange is embedded in the sealing ring.
5. The button cell of claim 1, wherein: and the periphery of the opening of the bottom shell is provided with a roller pressing edge which is turned inwards, and the roller pressing edge is turned inwards and downwards to press the sealing ring.
6. A process for manufacturing a high-temperature-resistant button cell according to any one of claims 1 to 5, which is characterized in that: the manufacturing process comprises the following steps:
step S1, preparing materials: preparing a bottom shell, an upper cover, an inner core and a polytetrafluoroethylene material;
step S2, molding: molding the polytetrafluoroethylene material to form a sealing ring by a molding process, and embedding the upper cover in the sealing ring during molding;
step S3, sintering: heating the preformed product to a temperature above the melting point, and sintering;
step S4, cooling: reducing the sintering temperature to room temperature;
step S5, rolling: the battery cell, the sealing ring and the upper cover are arranged in the bottom shell, the battery cell is communicated with the upper cover and the bottom shell through extrusion, the periphery of the bottom shell is turned inwards to form a roll pressing edge, and the sealing ring is pressed through the roll pressing edge.
7. The manufacturing process of the high-temperature-resistant button cell as claimed in claim 6, which is characterized in that: the polytetrafluoroethylene material is polytetrafluoroethylene powder with the particle size of 20-500 microns, and the polytetrafluoroethylene powder is sieved by a screen with 8-20 meshes before use.
8. The manufacturing process of the high-temperature-resistant button cell as claimed in claim 6, which is characterized in that: the step S2 includes the following sub-steps:
step S2-1, mixing materials: mixing polytetrafluoroethylene powder with other additives, wherein the weight ratio of the polytetrafluoroethylene powder to the other additives is 100: 18-25, mixing materials by using a container rotary mixer, wherein the rotating speed of the container is about 15-20 rpm, and the mixing time is 10-20 min;
step S2-2, preforming: and uniformly adding the mixed polytetrafluoroethylene powder into a mold, pressing the mixed polytetrafluoroethylene powder into a compact preformed product at normal temperature, placing an upper cover in the mold according to a preset shape during preforming, placing the polytetrafluoroethylene PTFE powder into the mold, and performing mold pressing, wherein the preforming pressure adopted during mold pressing is 17-35 MPa, and the pressure is maintained for 10-15 minutes.
9. The manufacturing process of the high-temperature-resistant button cell as claimed in claim 6, which is characterized in that: and S3, wherein the temperature rise speed is 80-120 ℃/h during sintering, the suspension method sintering or the dispersion method sintering is adopted during sintering, the polytetrafluoroethylene suspension method resin sintering temperature is 370-380 ℃, the dispersion method resin sintering temperature is 360-370 ℃, and when the temperature rise reaches the set temperature, the temperature is kept for 45-75 minutes.
10. The manufacturing process of the high-temperature-resistant button cell as claimed in claim 6, which is characterized in that: the temperature is reduced at a low speed of 15-25 ℃/hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010253162.1A CN111430594A (en) | 2020-04-02 | 2020-04-02 | High-temperature-resistant button battery and manufacturing process thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010253162.1A CN111430594A (en) | 2020-04-02 | 2020-04-02 | High-temperature-resistant button battery and manufacturing process thereof |
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| CN111430594A true CN111430594A (en) | 2020-07-17 |
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| CN202010253162.1A Pending CN111430594A (en) | 2020-04-02 | 2020-04-02 | High-temperature-resistant button battery and manufacturing process thereof |
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| 未知: "《http://www.sdcx.net/html/xsgfz/hyzs/2016/1130/6480.html》", 30 November 2016 * |
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