CN110265613B - Upper gasket of cylindrical lithium ion battery - Google Patents
Upper gasket of cylindrical lithium ion battery Download PDFInfo
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- CN110265613B CN110265613B CN201910497778.0A CN201910497778A CN110265613B CN 110265613 B CN110265613 B CN 110265613B CN 201910497778 A CN201910497778 A CN 201910497778A CN 110265613 B CN110265613 B CN 110265613B
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- lithium ion
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an upper gasket of a cylindrical lithium ion battery, which is a sheet with the shape matched with the cross section of an inner cavity of the lithium ion battery, the sheet is made of a modified rubber material, a prolate anode lug through hole is arranged in the middle of the sheet, and a plurality of side holes for electrolyte permeation are arranged at the position close to the outer edge of the sheet and surround the anode lug through hole. The through holes for the penetration of the electrolyte are formed in the center and the outer edge of the sheet, so that the problem of uneven penetration of the electrolyte is solved; the positive tab can be arranged at the U-shaped opening after penetrating through the positive tab through hole, so that the potential safety hazard of short circuit between the positive tab and the negative plate of the battery cell is effectively avoided; gas can be generated in the battery cell during charging, and the through holes on the thin sheet are distributed more uniformly, so that the gas is more favorably discharged; meanwhile, the sheet is made of modified rubber materials, so that the upper gasket has excellent temperature resistance, oil resistance and solvent resistance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an upper gasket of a cylindrical lithium ion battery.
Background
In a sealed secondary battery, a battery element including an electrode group including a positive electrode plate, a negative electrode plate, and a separator disposed between the positive electrode plate and the negative electrode plate, and an electrolyte solution for impregnating the electrode group is generally housed in a battery case (outer case) having an opening in a part thereof, and is sealed by a sealing member for sealing the opening of the battery case. In the sealed secondary battery, for example, a gasket is provided at a contact point between the positive electrode plate and the electrically connected positive electrode terminal and a contact point between the negative electrode plate and the electrically connected negative electrode terminal in order to prevent a short circuit between the pair of terminals and prevent leakage of the electrolyte. The gasket is required to have electrolyte resistance to the electrolyte solution and excellent airtightness.
The traditional upper gasket is only provided with a round hole with the diameter of 6-8mm at the center. This results in uneven electrolyte penetration, and the positive tab is likely to contact with the cell or the steel can to cause short circuit, which causes danger. Meanwhile, the traditional upper gasket is made of polyamide resin, polyarylene sulfide resin or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, and the like, and the resin has the defects of electrolyte resistance and heat resistance, so that the service life of the gasket is influenced.
Disclosure of Invention
The invention aims to provide an upper gasket of a cylindrical lithium ion battery, which is characterized in that through holes for electrolyte to permeate are formed in the center and the outer edge of a sheet, so that the problem of uneven electrolyte permeation is solved; the positive tab can be arranged at the U-shaped opening after penetrating through the positive tab through hole, so that the potential safety hazard of short circuit between the positive tab and the negative plate of the battery cell is effectively avoided; gas can be generated in the battery cell during charging, and the through holes on the thin sheet are distributed more uniformly, so that the gas is more favorably discharged; meanwhile, the sheet is made of modified rubber materials, so that the upper gasket has excellent temperature resistance, oil resistance and solvent resistance.
The purpose of the invention can be realized by the following technical scheme:
a cylindrical lithium ion battery upper gasket is a thin sheet with the shape matched with the cross section of an inner cavity of a lithium battery, the thin sheet is made of a modified rubber material, an oblong positive electrode tab through hole is formed in the middle of the thin sheet, and a plurality of side holes for electrolyte permeation are formed near the outer edge of the thin sheet and surround the positive electrode tab through hole;
the modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and the aramid fiber pulp according to the mass ratio of 1:2-3, adding the treatment liquid, stirring for 3-4h at 200r/min, filtering, and drying the solid in a vacuum drying oven at 150 ℃ to obtain a pretreated filler;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90And the second-stage vulcanization condition is 230 ℃ multiplied by 16h to obtain the modified rubber material.
Furthermore, the side holes (3) are distributed around the positive lug through holes (2) in a U shape.
Further, the side holes (3) are circular and at least six in number.
Furthermore, the positive lug through hole (2) is arranged at the center of the sheet (1) and is deviated to the U-shaped opening.
Furthermore, a central auxiliary hole (4) for electrolyte permeation is arranged beside the positive tab through hole (2), and the central auxiliary hole (4) is arranged on one side, away from the U-shaped opening, of the positive tab through hole (2).
Furthermore, the addition of the treatment liquid in the preparation process of the modified rubber material is 2-2.2 times of the mass of the aramid pulp.
Further, in the preparation process of the modified rubber material, the weight ratio of the fluororubber to the acid absorbent to the processing aid to the pretreated filler to the vulcanizing agent is (100: 0.6-0.8: 1-2): 8-10: 1.6-2; the vulcanizing agent is dicumyl peroxide.
The invention has the beneficial effects that:
the through holes for the penetration of the electrolyte are formed in the center and the outer edge of the sheet, so that the problem of uneven penetration of the electrolyte is solved; the positive tab can be arranged at the U-shaped opening after penetrating through the positive tab through hole, so that the potential safety hazard of short circuit between the positive tab and the negative plate of the battery cell is effectively avoided; gas can be generated in the battery cell during charging, and the through holes on the thin sheet are distributed more uniformly, so that the gas is more favorably discharged;
the sheet is made of a modified rubber material, the modified rubber material takes fluororubber as a matrix, the fluororubber has the characteristics of heat resistance, oil resistance, solvent resistance, strong oxidant resistance and the like and good physical properties, and the fluororubber is used as the matrix material of the gasket, so that the gasket has excellent heat resistance, electrolyte resistance and the like; the surface of the fibrous sepiolite contains Si-OH groups and Bronsted-Lewis acid centers, and has higher chemical activity, dicumyl peroxide is carboxyl-free peroxide and is sensitive to acid, and the fibrous sepiolite is easy to decompose more free radicals so as to increase the vulcanization speed; moreover, the aramid pulp is used as high-modulus fiber, has good toughness, does not reduce the length-diameter ratio of the pulp in a violent mixing processing process, is a short fiber material subjected to surface fibrillation treatment, and provides good mechanical interlocking property and interface bonding property for bonding with a rubber matrix by unique numerous branched structures on main fiber, so that the aramid pulp has a good compounding effect with fluororubber, the hardness and the stress at definite elongation of vulcanized rubber can be remarkably improved, and the high-temperature resistance of a rubber material can also be improved.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a gasket on a cylindrical lithium ion battery according to the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A cylindrical lithium ion battery upper gasket is shown in figure 1 and is a thin sheet 1 with the shape matched with the cross section of an inner cavity of a lithium battery, the thin sheet 1 is made of a modified rubber material, a prolate positive electrode lug through hole 2 is arranged in the middle of the thin sheet 1, and a plurality of side holes 3 for electrolyte permeation are arranged near the outer edge of the thin sheet and surround the positive electrode lug through hole 2;
the side holes 3 are distributed around the positive lug through hole 2 in a U shape;
the side holes 3 are circular and at least six in number;
the positive lug through hole 2 is arranged at the central U-shaped opening of the sheet 1;
a central auxiliary hole 4 for electrolyte permeation is arranged beside the positive lug through hole 2, and the central auxiliary hole 4 is preferably arranged on one side of the positive lug through hole 2, which is far away from the U-shaped opening;
in the specific implementation process, the positive tab can be arranged at the U-shaped opening after penetrating through the positive tab through hole 2, so that the potential safety hazard of short circuit between the positive tab and the negative plate of the battery cell is effectively avoided; through holes for electrolyte to permeate are formed in the center and the outer edge of the sheet 1, so that the problem of uneven electrolyte permeation is solved; gas can be generated in the battery cell during charging, and the through holes on the thin sheet are distributed more uniformly, so that the gas is more favorably discharged;
the modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and aramid pulp according to the mass ratio of 1:2-3, adding the treatment liquid, stirring for 3-4h at 200r/min, filtering, and drying the solid in a vacuum drying oven at 150 ℃ to obtain a pretreated filler;
wherein the addition amount of the treatment liquid is 2-2.2 times of the mass of the aramid fiber pulp;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
wherein the weight ratio of the fluororubber to the acid absorbent to the processing aid to the pretreated filler to the vulcanizing agent is 100:0.6-0.8: 1-2: 8-10: 1.6-2; the vulcanizing agent is dicumyl peroxide;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90Obtaining a modified rubber material under the second-stage vulcanization condition of 230 ℃ multiplied by 16 h;
the fluororubber has the characteristics of heat resistance, oil resistance, solvent resistance, strong oxidant resistance and the like and good physical properties, and is used as a base material of the gasket, so that the gasket has excellent heat resistance, electrolyte resistance and the like; the surface of the fibrous sepiolite contains Si-OH groups and Bronsted-Lewis acid centers, and has higher chemical activity, dicumyl peroxide is carboxyl-free peroxide and is sensitive to acid, and the fibrous sepiolite is easy to decompose more free radicals so as to increase the vulcanization speed; moreover, the aramid pulp is used as high-modulus fiber, has good toughness, does not reduce the length-diameter ratio of the pulp in a violent mixing processing process, is a short fiber material subjected to surface fibrillation treatment, and provides good mechanical interlocking property and interface bonding property for bonding with a rubber matrix by unique numerous branched structures on main fiber, so that the aramid pulp has a good compounding effect with fluororubber, the hardness and the stress at definite elongation of vulcanized rubber can be remarkably improved, and the high-temperature resistance of a rubber material can also be improved.
Example 1
The modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and the aramid pulp according to the mass ratio of 1:2, adding the treatment liquid, stirring for 3 hours at the speed of 200r/min, filtering, and drying the solid in a vacuum drying oven at the temperature of 150 ℃ to obtain a pretreated filler;
wherein the addition amount of the treatment liquid is 2 times of the mass of the aramid pulp;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
wherein the weight ratio of the fluororubber to the acid absorbent to the processing aid to the pretreated filler to the vulcanizing agent is 100:0.6: 1: 8: 1.6; the vulcanizing agent is dicumyl peroxide;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90And the second-stage vulcanization condition is 230 ℃ multiplied by 16h to obtain the modified rubber material.
Example 2
The modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and the aramid fiber pulp according to the mass ratio of 1:2.5, adding the treatment liquid, stirring for 3.5 hours at 200r/min, filtering, and drying the solid in a vacuum drying oven at 150 ℃ to obtain a pretreated filler;
wherein the addition amount of the treatment liquid is 2.1 times of the mass of the aramid pulp;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
wherein the weight ratio of the fluororubber to the acid absorbent to the processing aid to the pretreated filler to the vulcanizing agent is 100:0.7: 1.5: 9: 1.8; the vulcanizing agent is dicumyl peroxide;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90And the second-stage vulcanization condition is 230 ℃ multiplied by 16h to obtain the modified rubber material.
Example 3
The modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and aramid pulp according to the mass ratio of 1:3, adding the treatment liquid, stirring for 4 hours at 200r/min, filtering, and drying the solid in a vacuum drying oven at 150 ℃ to obtain a pretreated filler;
wherein the addition amount of the treatment liquid is 2.2 times of the mass of the aramid pulp;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
wherein the weight ratio of the fluororubber to the acid absorbent to the processing aid to the pretreated filler to the vulcanizing agent is 100:0.8: 2: 10: 2; the vulcanizing agent is dicumyl peroxide;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90And the second-stage vulcanization condition is 230 ℃ multiplied by 16h to obtain the modified rubber material.
Comparative example 1
In the second step of example 1, the fibrous sepiolite raw material was changed to aramid pulp.
Comparative example 2
The pretreated filler material in the third step of example 1 was removed.
Comparative example 3
Gasket materials on common commercial lithium ion batteries.
The following property tests were carried out on the materials obtained in examples 1 to 3 and comparative examples 1 to 3:
and (3) testing mechanical properties: the mechanical property is measured by adopting a GMT-4104 type microcomputer-controlled electronic universal tester, and the tensile property is tested according to GB/T9431-2000 plastic bending property test method; shore hardness is tested according to GB/T-1992; compression set property: testing the compression set of the composite material by GB/T7759 'determination of compression set of vulcanized rubber or thermoplastic rubber'; the crosslink density was determined and the results are shown in the following table:
it is understood that the tensile strength of the materials obtained in examples 1 to 3 is 7.89 to 7.96MPa,the elongation at break is 230.51-230.67%, and the Share A hardness is 72.5-72.8, which shows that the gasket material prepared by the invention has excellent mechanical properties; the materials obtained in examples 1 to 3 had compression set of 10.7 to 11.0% and a crosslink density of 93.1 to 93.4 mol/cm-3The fibrous sepiolite has a synergistic enhancement effect on the aramid pulp, is beneficial to the dispersion of the aramid pulp and improves the vulcanization performance of the rubber material by combining with the comparative example 1; in combination with comparative example 2, the addition of the filler had an effective reinforcing effect.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The upper gasket of the cylindrical lithium ion battery is characterized by being a thin sheet (1) with the shape matched with the cross section of an inner cavity of the lithium ion battery, wherein the thin sheet (1) is made of a modified rubber material, a prolate positive lug through hole (2) is formed in the middle of the thin sheet (1), and a plurality of side holes (3) for electrolyte permeation are formed in the position, close to the outer edge of the thin sheet, of the thin sheet and surround the positive lug through hole (2);
the modified rubber material is prepared by the following method:
firstly, adding a silane coupling agent KH-550 into acetone according to the volume ratio of 1:20 to obtain a treatment solution;
secondly, mixing the fibrous sepiolite and aramid pulp according to the mass ratio of 1:2-3, adding the treatment liquid, stirring for 3-4h at 200r/min, filtering, and drying the solid in a vacuum drying oven at 150 ℃ to obtain a pretreated filler;
thirdly, sequentially adding the fluororubber, the acid absorbent, the processing aid, the pretreated filler and the vulcanizing agent into an open mill, cutting 3 knives respectively at 3/4 left and right after the materials are eaten, beating a triangular bag for 6 times in a thin pass mode, and exhausting and discharging to obtain a rubber compound;
fourthly, standing the mixed rubber for 12h, and vulcanizing on a flat vulcanizing machine under the first-stage vulcanization condition of 170 ℃/15MPa x t90Obtaining a modified rubber material under the second-stage vulcanization condition of 230 ℃ multiplied by 16 h;
the vulcanizing agent is dicumyl peroxide.
2. The upper gasket of claim 1, wherein the side holes (3) are distributed around the through holes (2) of the positive tab in a U shape.
3. The upper gasket for a cylindrical lithium ion battery according to claim 1, wherein the side holes (3) are circular and have a number of at least six.
4. The upper gasket of the cylindrical lithium ion battery as claimed in claim 1, wherein the through hole (2) of the positive tab is disposed at the opening of the sheet (1) which is biased to a U-shape.
5. The upper gasket of the cylindrical lithium ion battery according to claim 1, wherein a central auxiliary hole (4) for electrolyte permeation is provided beside the through hole (2) of the positive tab, and the central auxiliary hole (4) is provided on the side of the through hole (2) of the positive tab far from the U-shaped opening.
6. The upper gasket of the cylindrical lithium ion battery as claimed in claim 1, wherein the addition amount of the treatment liquid in the preparation process of the modified rubber material is 2-2.2 times of the mass of the aramid pulp.
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| CN201910497778.0A CN110265613B (en) | 2019-06-10 | 2019-06-10 | Upper gasket of cylindrical lithium ion battery |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH108036A (en) * | 1996-06-25 | 1998-01-13 | Akebono Brake Ind Co Ltd | Non-asbestos-based friction material |
| CN201178104Y (en) * | 2008-01-29 | 2009-01-07 | 天津力神电池股份有限公司 | Isolative upper spacer for lithium ionic cell |
| CN103613886A (en) * | 2013-11-05 | 2014-03-05 | 广州机械科学研究院有限公司 | High temperature and high pressure-resistant fluororubber material, and preparation method and application thereof |
| CN203850368U (en) * | 2014-05-30 | 2014-09-24 | 福建金柏夷能源科技有限公司 | Upper insulation sheet |
| CN109370117A (en) * | 2018-08-09 | 2019-02-22 | 安徽中宏线缆有限公司 | A kind of ageing-resistant fluorubber cable sheath material of high fire-retardance |
-
2019
- 2019-06-10 CN CN201910497778.0A patent/CN110265613B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH108036A (en) * | 1996-06-25 | 1998-01-13 | Akebono Brake Ind Co Ltd | Non-asbestos-based friction material |
| CN201178104Y (en) * | 2008-01-29 | 2009-01-07 | 天津力神电池股份有限公司 | Isolative upper spacer for lithium ionic cell |
| CN103613886A (en) * | 2013-11-05 | 2014-03-05 | 广州机械科学研究院有限公司 | High temperature and high pressure-resistant fluororubber material, and preparation method and application thereof |
| CN203850368U (en) * | 2014-05-30 | 2014-09-24 | 福建金柏夷能源科技有限公司 | Upper insulation sheet |
| CN109370117A (en) * | 2018-08-09 | 2019-02-22 | 安徽中宏线缆有限公司 | A kind of ageing-resistant fluorubber cable sheath material of high fire-retardance |
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| CN110265613A (en) | 2019-09-20 |
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