CN109082047B - Pole sealing material of lithium ion battery and preparation method thereof - Google Patents
Pole sealing material of lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN109082047B CN109082047B CN201810512707.9A CN201810512707A CN109082047B CN 109082047 B CN109082047 B CN 109082047B CN 201810512707 A CN201810512707 A CN 201810512707A CN 109082047 B CN109082047 B CN 109082047B
- Authority
- CN
- China
- Prior art keywords
- parts
- rubber
- sealing material
- lithium battery
- fluororubber
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a pole sealing material of a lithium battery and a preparation method thereof. The invention takes the fluororubber as the main matrix, and is matched with auxiliary materials such as auxiliary rubber, conductive filler, processing aid, peroxide vulcanizing agent, auxiliary crosslinking agent and the like, and the high-conductivity rubber composite material with low compression permanent deformation is prepared by mixing through an open mill or an internal mixer, so that the consumption of the conductive filler is reduced under the condition of ensuring low resistance and excellent electrolyte resistance, and the composite material has both low compression permanent deformation and high conductivity. The material prepared by the invention has excellent electric conduction and voltage transformation characteristics, and the volume resistance is 102Ω·cm～104The material has high-temperature compression permanent deformation of less than 30% (150 ℃ C. 70h) between omega cm, has excellent physical and mechanical properties and heat resistance, aging resistance and electrolyte resistance, and is very suitable for sealing the conductive pole column of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of modified rubber, in particular to a pole sealing material of a lithium ion battery and a preparation method thereof.
Background
Conductive rubber is generally referred to as having a volume resistance of 109Rubber material within omega cm, however, the rubber is an excellent insulating material, and the volume resistance is generally more than 1014Omega cm, the volume resistance of which is to be reduced to 104The production is stable in mass production and has a large difficulty. At present, conductive PPS plastic is generally used in the market as a conductive material of a positive pole column of a lithium ion battery, and although the conductive PPS plastic has relatively low conductivity, the conductive PPS plastic does not meet the lightweight requirement of the conventional lithium ion battery pack, and the conductive PPS plastic has long service life, high reliability and high cost. In addition, the existing positive pole column is sealed by adopting a sealing mode of PPS plastic matched with insulating rubber materialHowever, it increases the complexity of the sealing structure, which is not favorable for the overall optimization of the battery structure.
In the patent application No. 201110128961.7, "low-density high-strength conductive rubber and a preparation method thereof", a conductive material using silicone rubber as a base has relatively excellent heat resistance and relatively low volume resistivity (0.02-0.6 Ω · cm), but has very low tensile strength (2.8-3.6 MPa) and is not resistant to chemical media.
The patent application No. 201110248397.2 discloses a conductive rubber, which uses natural rubber as a conductive matrix, has high tensile strength (not less than 25MPa) and good aging resistance, but has high conductive resistivity (from rubber to metal is not more than 500k omega when the conductive voltage is 500V), and is not resistant to electrolyte.
An EPDM-based conductive rubber and a preparation method thereof disclosed in patent application No. 201210038416.3, wherein an ethylene propylene rubber-based conductive material has very excellent electrolyte resistance and very low resistivity (0.02-0.09 Ω & cm), but has very low tensile strength (1MPa) and poor high-temperature voltage transformation performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the pole sealing material of the lithium ion battery and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the pole sealing material for the lithium battery comprises the following components in parts by weight: 50-90 parts of fluororubber, 10-50 parts of auxiliary rubber, 9-18 parts of conductive filler, 1.25-5 parts of processing aid, 1-3 parts of peroxide vulcanizing agent and 2-4 parts of auxiliary crosslinking agent.
The invention designs the conductive rubber formula by using the fluororubber as the base material for the first time, fully utilizes the inherent characteristics of various chemical media such as high temperature resistance, electrolyte resistance and the like, weather resistance, weather aging resistance, excellent high-temperature pressure change and the like of the fluororubber material, and adjusts the hardness of the material by compounding with the auxiliary rubberThe processing performance of the rubber compound is improved, and the resistance stability of the material is improved; compared with the existing conductive rubber, the conductive rubber provided by the invention is added with less conductive materials, so that the controllable hardness of the rubber compound is ensured, and simultaneously, the high conductivity is also ensured. By compounding the components, the pole sealing material obtained by the invention not only has lower volume resistance (10)2～104Omega cm) and higher resistance stability, and also has excellent electrolyte resistance and low compression set.
The preferable embodiment of the pole sealing material of the lithium battery comprises the following components in parts by weight: 70-75 parts of fluororubber, 25-30 parts of auxiliary rubber, 11-15 parts of conductive filler, 3-3.5 parts of processing aid, 1.5-3 parts of peroxide vulcanizing agent and 2-2.5 parts of auxiliary crosslinking agent.
Through multiple tests, the inventor researches the compounding relationship of each component, optimizes the formula of the pole sealing material, further improves the tensile strength, the resistance stability and the electrolyte resistance of the pole sealing material, and reduces the volume resistance.
In a preferred embodiment of the sealing material for a lithium battery terminal according to the present invention, the fluororubber is peroxide-vulcanized fluororubber.
Compared with bisphenol fluororubbers, peroxide vulcanized fluororubbers have better electrolyte resistance.
As a preferred embodiment of the pole sealing material of the lithium battery, the Mooney viscosity [ ML (1+10)121 ℃) of the peroxide vulcanized fluororubber is 17-33, and the fluorine content is 69-71 wt%.
In a preferred embodiment of the sealing material for a terminal post of a lithium battery according to the present invention, the auxiliary rubber is ethylene propylene rubber.
According to the technical scheme, the ethylene propylene rubber is preferably selected, the hardness of the material is further adjusted, the processability of the rubber compound is improved, and the strong polarity of the fluororubber and the non-polarity of the ethylene propylene rubber are integrated by utilizing the more excellent electrolyte resistance and aging resistance of the ethylene propylene rubber, so that the influence of either party on the stability of the conductivity is eliminated.
The inventor researches a vulcanization crosslinking system of the fluororubber and the ethylene propylene rubber, further preferably selects peroxide vulcanized fluororubber, and promotes the fluororubber and the ethylene propylene rubber to realize co-vulcanization.
As a preferred embodiment of the pole sealing material of the lithium battery, the Mooney viscosity [ ML (1+4)100 ℃ C ] of the ethylene propylene rubber is 8-55, and the ethylene content is 45-54 wt%.
According to the technical scheme, the low-Mooney ethylene propylene rubber is preferably selected, so that the processability of the rubber compound is further improved.
In a preferred embodiment of the sealing material for a terminal of a lithium battery according to the present invention, the processing aid is at least one of an aliphatic hydrocarbon derivative, a wax, an organosilicon compound, magnesium aluminum hydrotalcite, a fatty acid derivative, and a metal soap; the conductive material is conductive carbon black.
According to the invention, through optimizing the compound processing aid, the dispersion degree of each powder in the rubber matrix and the affinity between the fluororubber and the auxiliary rubber are improved, the uniform blending of the fluororubber and the auxiliary rubber is promoted, and the processing performance of the rubber compound is optimized.
The conductive carbon black is screened and filled in a small amount as the conductive filler, so that the controllable hardness of the rubber compound is ensured, and simultaneously, the high conductivity is also ensured, and the traditional filling of the conductive fillers such as carbon nano tubes, graphene, carbon fibers and the like can cause the rapid increase of the hardness of the rubber compound, is not beneficial to processing and production, and reduces the possibility of realizing final industrial mass production.
Further, the fatty acid derivative includes a mixture of natural fatty acid calcium salt and amide fatty wax.
Further, the conductive filler is at least one of superconducting carbon black or weakly conductive carbon black; the BET specific surface area of the superconducting carbon black is 1000m2(ii)/g, the weakly conductive carbon black has a BET specific surface area of 800m2/g。
In a preferred embodiment of the terminal sealing material for a lithium battery according to the present invention, the peroxide curing agent is at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane and dicumyl peroxide.
In a preferred embodiment of the terminal sealing material for a lithium battery according to the present invention, the auxiliary crosslinking agent is at least one of triallyl isocyanurate and N, N' -m-phenylene bismaleimide.
The invention also provides a preparation method of the pole sealing material of the lithium battery, which comprises the following steps:
(1) uniformly blending the fluororubber and the auxiliary rubber;
(2) sequentially adding conductive filler, part of processing aid and auxiliary crosslinking agent for one-time rubber mixing, and standing for more than 4 hours;
(3) adding the rest processing aid and peroxide vulcanizing agent for secondary rubber mixing;
(4) performing secondary vulcanization treatment on the mixture treated in the step (3), wherein the primary vulcanization temperature is 150-170 ℃, and the vulcanization time is 3-10 min; the second-stage vulcanization temperature is 140-170 ℃, and the vulcanization time is 1-8 h.
Further, in the step (4), a vacuum vulcanization treatment is adopted.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the fluororubber is used as the base material for the first time to design the conductive rubber formula, the inherent characteristics of the fluororubber material such as high temperature resistance, electrolyte resistance and various other chemical media, weather resistance, aging resistance, excellent high-temperature pressure change and the like are fully utilized, the hardness of the material is adjusted by compounding with the auxiliary rubber, the processability of the rubber compound is improved, and the resistance stability of the material is improved. Compared with the existing conductive rubber, the conductive rubber provided by the invention is added with less conductive filler, so that the controllable hardness of the rubber compound is ensured, and simultaneously, the high conductivity is also ensured. The conductive material prepared by the invention not only has lower volume resistance (10)2～104Omega cm), has higher resistance stability, excellent electrolyte resistance and low compression permanent deformation performance, and is very suitable for replacing the PPS material used as weak conductive sealing in the existing lithium battery of the new energy automobile.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1
As an embodiment of the terminal sealing material for a lithium battery of the present invention, the terminal sealing material for a lithium battery of the present embodiment includes the following components in parts by mass: 70 parts of fluororubber, 30 parts of ethylene propylene rubber, 7 parts of superconducting carbon black, 6 parts of weak conductive carbon black, 3 parts of a mixture of natural fatty acid calcium salt and amide ester wax, 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 0.5 part of dicumyl peroxide and 2.5 parts of triallyl isocyanurate.
The BET specific surface area of the superconducting carbon black described in this example was 1000m2(ii)/g, the weakly conductive carbon black has a BET specific surface area of 800m2/g。
The preparation method of the pole sealing material of the lithium battery comprises the following steps:
1. beating the roll pitch of an open mill to 3mm, wrapping a roll with fluororubber, cutting left and right for 2 times, dividing ethylene propylene rubber into small blocks, slowly adding the small blocks, mixing the two rubbers uniformly, sequentially adding a conductive filler, an auxiliary cross-linking agent and part of processing aids, after powder is eaten, cutting left and right for 2 times, beating the roll pitch of the open mill to 1mm, wrapping a rubber material with a triangular bag for 5 times, re-adjusting the roll pitch of the open mill to 3mm, turning over the rubber turning machine for 5min, and then placing a lower sheet for more than 4 h;
2. beating the roll pitch of the open mill to the position of 3mm, wrapping the roll again after primary rubber mixing, sequentially adding peroxide and the rest processing aid, cutting the roll 2 times after powder feeding, beating the roll pitch of the open mill to 1mm, wrapping the roll with the rubber material, wrapping the roll with a triangle for 5 times, adjusting the roll pitch of the open mill to 3mm again, and discharging the sheet after turning the rubber material for 5 min;
3. putting the mixed rubber compound into a mould, vulcanizing for 10min at 170 ℃ on a flat vulcanizing machine, then placing for 4 hours in a high-temperature oven at constant temperature of 150 ℃, taking out, and carrying out sheet-making detection, wherein the properties of the vulcanized rubber are shown in Table 1:
TABLE 1
The inventor finds that, in the embodiment, the superconducting carbon black and the weak conductive carbon black are replaced by the conductive fillers such as the carbon nanotubes, the graphene, the carbon fibers and the like, and compared with the conductive carbon black, the filling of the carbon nanotubes, the graphene and the carbon fibers can cause the hardness of the rubber compound to be rapidly increased, so that the processing and the production are not facilitated, and the possibility of realizing the final industrial mass production is reduced. Meanwhile, the cost of the carbon nano tube, the graphene, the carbon fiber and the like is too high, and the compression permanent deformation performance of the material is greatly reduced.
In this embodiment, if the ethylene propylene rubber is replaced with the auxiliary rubber such as fluorosilicone rubber, silicone rubber, etc., although the thermal aging resistance and the high-temperature compression set resistance of the ethylene propylene rubber are improved, the key electrolyte resistance is significantly reduced, and the volume and mass change after electrolyte resistance is large.
Example 2
As an embodiment of the terminal sealing material for a lithium battery of the present invention, the terminal sealing material for a lithium battery of the present embodiment includes the following components in parts by mass: 75 parts of peroxide vulcanized fluororubber, 25 parts of ethylene propylene rubber, 11 parts of superconducting carbon black, 1 part of aliphatic hydrocarbon processing aid, 1 part of wax processing aid, 1 part of organic silicon compound, 0.5 part of magnesium aluminum hydrotalcite, 1 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 0.5 part of dicumyl peroxide, 1 part of triallyl isocyanurate and 1 part of N, N' -m-phenylene bismaleimide.
Mooney viscosity [ ML (1+10)121 ℃ C ] of the peroxide-cured fluororubber in this example]17-33, and the fluorine content is 69-71 wt%; mooney viscosity [ ML (1+4)100 ℃ C ] of the ethylene-propylene rubber]8-55, and the ethylene content is 45-54 wt%; the BET specific surface area of the superconducting carbon black is 1000m2(ii)/g, the weakly conductive carbon black has a BET specific surface area of 800m2/g。
The preparation method of the pole sealing material of the lithium battery comprises the following steps:
1. firstly, putting peroxide vulcanized fluororubber into an internal mixer for plastication, adding ethylene propylene rubber for continuous mixing when the temperature is raised to 50 ℃, adding conductive filler for mixing when the temperature is raised to 70 ℃, adding an auxiliary crosslinking agent and part of processing aid when the temperature is raised to 90 ℃ after current is stabilized, and discharging rubber when the temperature is raised to 100 ℃;
2. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the roll with the rubber material for 5 times of triangular wrapping, adjusting the roll spacing to 5mm, and standing for more than 4 hours to obtain primary rubber compound;
3. adding the primary rubber compound into an internal mixer, carrying out internal mixing for 1min, raising the temperature to 50 ℃, extracting lump, turning rubber once, raising the temperature to 60 ℃, adding a peroxide vulcanizing agent, raising the temperature to 70 ℃, adding the rest of processing aids, and raising the temperature to 80 ℃ to discharge rubber;
4. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the rubber material with the roll for 5 times, and then, adjusting the roll spacing to 5mm and then, obtaining secondary rubber compound;
5. putting the mixed rubber compound into a mould, vulcanizing for 10min at 170 ℃ on a flat vulcanizing machine, then placing for 4 hours in a high-temperature oven at constant temperature of 150 ℃, taking out, and carrying out sheet-making detection, wherein the properties of the vulcanized rubber are shown in Table 2:
TABLE 2
Example 3
As an embodiment of the terminal sealing material for a lithium battery of the present invention, the terminal sealing material for a lithium battery of the present embodiment includes the following components in parts by mass: 72 parts of peroxide vulcanized fluororubber, 28 parts of ethylene propylene rubber, 15 parts of superconducting carbon black, 1 part of aliphatic hydrocarbon derivative, 0.5 part of organic silicon compound, 2 parts of magnesium-aluminum hydrotalcite, 1.5 parts of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1.5 parts of dicumyl peroxide, 1 part of triallyl isocyanurate and 1.5 parts of N, N' -m-phenylene bismaleimide.
Mooney viscosity [ ML (1+10)121 ℃ C ] of the peroxide-cured fluororubber in this example]17-33, and the fluorine content is 69-71 wt%; mooney viscosity [ ML (1+4)100 ℃ C ] of the ethylene-propylene rubber]8-55, and the ethylene content is 45-54 wt%; the BET specific surface area of the superconducting carbon black is 1000m2/g。
The preparation method of the pole sealing material of the lithium battery comprises the following steps:
1. beating the roll distance of an open mill to a position of 2mm, putting peroxide vulcanized fluororubber into a wrapping roll, dividing ethylene propylene rubber into small blocks, slowly adding the ethylene propylene rubber into the small blocks, simultaneously transferring the two blocks into an internal mixer to start plastication after the two blocks are completely mixed, adding a conductive filler for mixing when the temperature is raised to 60 ℃, raising the temperature to 90 ℃ after current is stabilized, adding an auxiliary crosslinking agent and part of processing aids, and discharging rubber after the temperature is raised to 100 ℃;
2. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the roll with the rubber material for 5 times of triangular wrapping, adjusting the roll spacing to 5mm, and standing for more than 4 hours to obtain primary rubber compound;
3. adding the primary rubber compound into an internal mixer, carrying out internal mixing for about 1min, raising the temperature to 50 ℃, extracting lumps, turning rubber once, raising the temperature to 60 ℃, adding a peroxide vulcanizing agent, raising the temperature to 70 ℃, adding the rest of processing aids, and raising the temperature to 80 ℃ to discharge rubber;
4. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the rubber material with the roll for 5 times, and then, adjusting the roll spacing to 5mm and then, obtaining secondary rubber compound;
5. putting the mixed rubber compound into a mould, vulcanizing for 10min at 170 ℃ on a flat vulcanizing machine, then placing for 4 hours in a high-temperature oven at constant temperature of 150 ℃, taking out, and carrying out sheet-making detection, wherein the properties of the vulcanized rubber are shown in Table 3:
TABLE 3
Example 4
As an embodiment of the terminal sealing material for a lithium battery of the present invention, the terminal sealing material for a lithium battery of the present embodiment includes the following components in parts by mass: 50 parts of peroxide vulcanized fluororubber, 50 parts of ethylene propylene rubber, 9 parts of superconducting carbon black, 0.5 part of aliphatic hydrocarbon derivative, 0.5 part of organic silicon compound, 0.25 part of magnesium aluminum hydrotalcite, 0.5 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 0.5 part of dicumyl peroxide, 2 parts of triallyl isocyanurate and 1.5 parts of N, N' -m-phenylene bismaleimide.
Mooney viscosity [ ML (1+10)121 ℃ C ] of the peroxide-cured fluororubber in this example]17-33, and the fluorine content is 69-71 wt%; mooney viscosity [ ML (1+4)100 ℃ C ] of the ethylene-propylene rubber]8-55, and the ethylene content is 45-54 wt%; the BET specific surface area of the superconducting carbon black is 1000m2/g。
The preparation method of the pole sealing material of the lithium battery comprises the following steps:
1. beating the roll distance of an open mill to a position of 2mm, putting peroxide vulcanized fluororubber into a wrapping roll, dividing ethylene propylene rubber into small blocks, slowly adding the ethylene propylene rubber into the small blocks, simultaneously transferring the two blocks into an internal mixer to start plastication after the two blocks are completely mixed, adding a conductive filler for mixing when the temperature is raised to 60 ℃, raising the temperature to 90 ℃ after current is stabilized, adding an auxiliary crosslinking agent and part of processing aids, and discharging rubber after the temperature is raised to 100 ℃;
2. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the roll with the rubber material for 5 times of triangular wrapping, adjusting the roll spacing to 5mm, and standing for more than 4 hours to obtain primary rubber compound;
3. adding the primary rubber compound into an internal mixer, carrying out internal mixing for about 1min, raising the temperature to 50 ℃, extracting lumps, turning rubber once, raising the temperature to 60 ℃, adding a peroxide vulcanizing agent, raising the temperature to 70 ℃, adding the rest of processing aids, and raising the temperature to 80 ℃ to discharge rubber;
4. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the rubber material with the roll for 5 times, and then, adjusting the roll spacing to 5mm and then, obtaining secondary rubber compound;
5. putting the mixed rubber compound into a mould, vulcanizing for 3min at 150 ℃ on a flat vulcanizing machine, then placing for 1 h in a high-temperature oven at a constant temperature of 170 ℃, taking out, and carrying out sheet-making detection, wherein the properties of the vulcanized rubber are shown in Table 4:
TABLE 4
Example 5
As an embodiment of the terminal sealing material for a lithium battery of the present invention, the terminal sealing material for a lithium battery of the present embodiment includes the following components in parts by mass: 90 parts of peroxide vulcanized fluororubber, 10 parts of ethylene propylene rubber, 10 parts of superconducting carbon black, 8 parts of weak conductive carbon black, 2 parts of aliphatic hydrocarbon derivatives, 2 parts of organic silicon compounds, 1 part of magnesium aluminum hydrotalcite, 1 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1.5 parts of dicumyl peroxide, 1 part of triallyl isocyanurate and 3 parts of N, N' -m-phenylene bismaleimide.
Mooney viscosity [ ML (1+10)121 ℃ C ] of the peroxide-cured fluororubber in this example]17-33, and the fluorine content is 69-71 wt%; mooney viscosity [ ML (1+4)100 ℃ C ] of the ethylene-propylene rubber]8-55, and the ethylene content is 45-54 wt%; the BET specific surface area of the superconducting carbon black is 1000m2(ii)/g, the weakly conductive carbon black has a BET specific surface area of 800m2/g。
The preparation method of the pole sealing material of the lithium battery comprises the following steps:
1. beating the roll distance of an open mill to a position of 2mm, putting peroxide vulcanized fluororubber into a wrapping roll, dividing ethylene propylene rubber into small blocks, slowly adding the ethylene propylene rubber into the small blocks, simultaneously transferring the two blocks into an internal mixer to start plastication after the two blocks are completely mixed, adding a conductive filler for mixing when the temperature is raised to 60 ℃, raising the temperature to 90 ℃ after current is stabilized, adding an auxiliary crosslinking agent and part of processing aids, and discharging rubber after the temperature is raised to 100 ℃;
2. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the roll with the rubber material for 5 times of triangular wrapping, adjusting the roll spacing to 5mm, and standing for more than 4 hours to obtain primary rubber compound;
3. adding the primary rubber compound into an internal mixer, carrying out internal mixing for 1min, raising the temperature to 50 ℃, extracting lump, turning rubber once, raising the temperature to 60 ℃, adding a peroxide vulcanizing agent, raising the temperature to 70 ℃, adding the rest of processing aids, and raising the temperature to 80 ℃ to discharge rubber;
4. adjusting the roll spacing of an open mill to 3-5 mm, transferring the rubber material refined by an internal mixer to the open mill, wrapping the roll, then, controlling a left cutter and a right cutter for 2 times, turning over the rubber turning machine for 5min, then, beating the roll spacing of the open mill to 1-2 mm, wrapping the rubber material with the roll for 5 times, and then, adjusting the roll spacing to 5mm and then, obtaining secondary rubber compound;
5. putting the mixed rubber compound into a mould, vulcanizing for 5min at 160 ℃ on a flat vulcanizing machine, then placing for 8 hours in a high-temperature oven at constant temperature of 140 ℃, taking out, and carrying out sheet-making detection, wherein the properties of the vulcanized rubber are shown in Table 5:
TABLE 5
The invention can also adopt metal soap surfactant as processing aid to improve the processing performance of the sizing material.
The pole sealing material for the lithium battery comprises the following components in parts by weight: 50-90 parts of fluororubber, 10-50 parts of auxiliary rubber, 9-18 parts of conductive filler, 1.25-5 parts of processing aid, 1-3 parts of peroxide vulcanizing agent and 2-4 parts of auxiliary crosslinking agent, and further, auxiliary materials such as 1-3 parts of acid acceptor, 0.3-5 parts of vulcanization accelerator and the like can be included.
In conclusion, the invention researches a sealing system of a lithium battery of a new energy automobile, develops a fluororubber material with high conductivity, excellent electrolyte resistance, weather resistance, medium and low hardness and low high-temperature voltage change, is used for replacing the PPS pole sealing which realizes weak conductivity in the new energy lithium battery at present, and truly meets the matched use function of the battery from the viewpoints of light weight, long service life, high reliability and structure optimization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The pole sealing material for the lithium battery is characterized by comprising the following components in parts by mass: 50-90 parts of fluororubber, 10-50 parts of auxiliary rubber, 9-18 parts of conductive filler, 1.25-5 parts of processing aid, 1-3 parts of peroxide vulcanizing agent and 2-4 parts of auxiliary crosslinking agent, wherein the fluororubber is peroxide vulcanized fluororubber, the auxiliary rubber is ethylene propylene rubber, and the conductive filler is conductive carbon black.
2. The pole sealing material for a lithium battery as claimed in claim 1, which comprises the following components in parts by mass: 70-75 parts of fluororubber, 25-30 parts of auxiliary rubber, 11-15 parts of conductive filler, 3-3.5 parts of processing aid, 1.5-3 parts of peroxide vulcanizing agent and 2-2.5 parts of auxiliary crosslinking agent.
3. The pole sealing material for a lithium battery as claimed in claim 1, wherein the peroxide-vulcanized fluororubber has a Mooney viscosity of 17 to 33 and a fluorine content of 69 to 71 wt.%.
4. The pole sealing material for a lithium battery as claimed in claim 1, wherein the ethylene-propylene rubber has a Mooney viscosity of 8 to 55 and an ethylene content of 45 to 54 wt%.
5. The pole sealing material of a lithium battery as claimed in claim 1, wherein the processing aid is at least one of aliphatic hydrocarbon derivatives, waxes, organosilicon compounds, magnesium aluminum hydrotalcite, fatty acid derivatives, and metal soaps.
6. The pole sealing material of a lithium battery as claimed in claim 1, wherein the peroxide curing agent is at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane and dicumyl peroxide.
7. The pole sealing material of a lithium battery as claimed in claim 1, wherein the co-crosslinking agent is at least one of triallyl isocyanurate and N, N' -m-phenylene bismaleimide.
8. The preparation method of the pole sealing material for the lithium battery as claimed in any one of claims 1 to 7, comprising the steps of:
(1) uniformly blending the fluororubber and the auxiliary rubber;
(2) sequentially adding conductive filler, part of processing aid and auxiliary crosslinking agent for one-time rubber mixing, and standing for more than 4 hours;
(3) adding the rest processing aid and peroxide vulcanizing agent for secondary rubber mixing;
(4) performing secondary vulcanization treatment on the mixture treated in the step (3), wherein the primary vulcanization temperature is 150-170 ℃, and the vulcanization time is 3-10 min; the second-stage vulcanization temperature is 140-170 ℃, and the vulcanization time is 1-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810512707.9A CN109082047B (en) | 2018-05-24 | 2018-05-24 | Pole sealing material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810512707.9A CN109082047B (en) | 2018-05-24 | 2018-05-24 | Pole sealing material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109082047A CN109082047A (en) | 2018-12-25 |
| CN109082047B true CN109082047B (en) | 2021-01-01 |
Family
ID=64839142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810512707.9A Active CN109082047B (en) | 2018-05-24 | 2018-05-24 | Pole sealing material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109082047B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269511A (en) * | 2020-03-18 | 2020-06-12 | 江苏中煜橡塑科技有限公司 | Insulating fluororubber material for sealing lithium battery and preparation method thereof |
| CN115434153B (en) * | 2022-09-21 | 2024-05-10 | 广东硕成科技股份有限公司 | Antistatic cloth coating adhesive cement and preparation method thereof |
| CN115584095B (en) * | 2022-10-31 | 2023-09-29 | 江苏中煜橡塑科技有限公司 | Method for preparing high-conductivity fluororubber sealing material by ionic liquid assisted dispersion |
| CN115926344B (en) * | 2022-12-31 | 2024-04-19 | 氟乐泰科（厦门）新材料有限公司 | Modified fluororubber compound and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009072606A1 (en) * | 2007-12-06 | 2009-06-11 | Daikin Industries, Ltd. | Peroxide-curable, electrically conductive fluoroelastomer composition |
-
2018
- 2018-05-24 CN CN201810512707.9A patent/CN109082047B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009072606A1 (en) * | 2007-12-06 | 2009-06-11 | Daikin Industries, Ltd. | Peroxide-curable, electrically conductive fluoroelastomer composition |
Non-Patent Citations (1)
| Title |
|---|
| 二元乙丙橡胶与四丙氟橡胶的并用研究;魏伯荣等;《特种橡胶制品》;19950812;第6-9、18页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109082047A (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109082047B (en) | Pole sealing material of lithium ion battery and preparation method thereof | |
| CN102030949A (en) | High-temperature resistant ethylene-propylene-diene monomer (EPDM) formula for lug of exhaust system and preparation method thereof | |
| CN107474376A (en) | A kind of cable semi-conductive shielding material and preparation method thereof | |
| CN105175911B (en) | A kind of Weatherproof ageing-resistant laminated rubber bearing elastomeric material | |
| CN105330990A (en) | Insulating material for new energy vehicle charging pile cable and preparation method of insulating material | |
| CN109456542A (en) | A kind of rubber insulation material | |
| CN104861273B (en) | Be used for composite of thermistor and its preparation method and application | |
| CN103059352A (en) | Sheath rubber for rubber sheath flexible cables | |
| CN103694710B (en) | A kind of heat-resisting Oil-Resistant Cable Sheath of rubber plastic blend and preparation method thereof | |
| CN106633435A (en) | Ethylene-propylene-diene-terpolymer rubber cold-contraction pipe suitable for high-temperature storage and low-temperature installation and preparation method | |
| CN108314898A (en) | Conductive rubber composition, conductive rubber and preparation method thereof | |
| CN105504467A (en) | Preparation process of high-tensile-strength insulating rubber cable material | |
| CN105111642B (en) | A kind of 4 third fluorubber with low compression set performance and preparation method thereof | |
| CN108610562B (en) | Low-pressure-change high-temperature-resistant ethylene propylene rubber material and preparation method thereof | |
| CN109082014A (en) | A kind of thermally conductive EPDM sebific duct and preparation method thereof | |
| CN104788826B (en) | A kind of mining ageing-resistant EPT rubber cable sheath material | |
| CN117050432A (en) | High-low temperature resistant and long-service life sealing rubber composite material and preparation method thereof | |
| JP5184454B2 (en) | Rubber composition with excellent low-temperature shrinkability | |
| CN101434747A (en) | Preparation of bamboo charcoal-based highly conductive rubber | |
| CN114672116B (en) | Low-compressive stress relaxation fluororubber for battery sealing element and preparation method thereof | |
| CN107337859A (en) | Oil-immersed pump electric power cable oil resistant EP rubbers sheath material and preparation method thereof | |
| CN115926344B (en) | Modified fluororubber compound and preparation method thereof | |
| JP2002069254A (en) | Peroxide crosslinkable rubber composition | |
| CN106065152A (en) | Hot high pressure elasto-plasticity insulating materials and preparation method thereof | |
| CN115602354A (en) | Light aluminum alloy wire harness for automobile and processing technology thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |