CN108929494A - A kind of ethylene propylene diene rubber and preparation method thereof for lithium ion battery thermal protection - Google Patents
A kind of ethylene propylene diene rubber and preparation method thereof for lithium ion battery thermal protection Download PDFInfo
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- CN108929494A CN108929494A CN201811012946.4A CN201811012946A CN108929494A CN 108929494 A CN108929494 A CN 108929494A CN 201811012946 A CN201811012946 A CN 201811012946A CN 108929494 A CN108929494 A CN 108929494A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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Abstract
A kind of thermally protective materials and preparation method thereof for lithium ion battery, the thermally protective materials, its raw material composition includes: ethylene propylene diene rubber, resin, fiber and auxiliary agent, and the auxiliary agent includes fire retardant and selected from one of plasticizer, activator, coupling agent, reinforcing agent, promotor, vulcanizing agent etc. or a variety of.The thermally protective materials significantly improve thermal protective performance of the lithium ion battery under the combustion case that happens suddenly, and by controlling temperature field, the periphery surface temperature of adjacent, similar lithium ion battery are reduced, to reduce the probability of its burning and explosion.
Description
Technical field
The invention belongs to field of functional materials, and in particular to a kind of ethylene-propylene-diene monomer for lithium ion battery thermal protection
Glue and its preparation method and application.
Background technique
Lithium ion battery is because it is high with energy density, have extended cycle life, energy efficiency is high, self discharge is small, memoryless effect
Should and it is pollution-free many advantages, such as, and be widely used in making in electric car and hybrid-electric car as power battery pack
With.Lithium ion battery applied by electric car and hybrid vehicle, often since its charging and discharging currents is big, radiating condition is poor,
Internal temperature of battery is caused to increase, to cause thermal runaway.Under conditions of abuse, lithium ion battery can be warming up to 700 DEG C of left sides
Phenomena such as right side easily causes chain exothermic reaction, and generation smolders, burns or even explodes.Since lithium ion battery security is poor
Factor, it is likely that immeasurable injury can be caused to test equipment and operator, in recent years the power electric of electric car
The safe incontrollable accidents of pond --- lithium ion battery frequently occur, so that various countries scientific research personnel asks the safety of lithium ion battery
Topic is more paid attention to.Therefore the anti-flaming thermal-insulation for carrying out exterior material to lithium ion battery for electric vehicle designs particularly significant.
Lithium ion battery thermal protection technology is to increase thermal insulation layer in battery pack, to block thermal runaway from monomer out of control to week
Monomer propagation is enclosed, the damage and subsidiary destruction of battery pack are reduced.Domestic heat management studies more concern at present
In terms of heat dissipation, such as battery system cabinet and mould group.Ideal ablation resistant material should have pyrolysis temperature is low, pyrolysis heat is big, at
The characteristics such as charcoal rate is high, material specific heat is big, thermal coefficient is small, density is low.The ablation resistant material base of China's research and application at this stage
Material mainly has the kinds such as epoxy resin, phenolic resin, polysulfide rubber.
EP rubbers be ethylene and propylene random copolymer (EPM) or again added with a small amount of non-conjugated diene for vulcanization point
The ternary atactic copolymer (EPDM) of monomer contains intermingle with production.EP rubbers dosage in synthetic rubber accounts for third position.EPDM master
To classify by polymerized monomer, it is also different, whether oil-filled, whether dirty with the ratio difference of propylene, mooney viscosity because of ethylene in every class
Dye etc. and point have the different trades mark.
The ratio of ethylene and propylene has a major impact the performance of EP rubbers, usually with the molar fraction table of propylene units
Show: the range of the molar fraction of propylene units is 22~60 in EPM；In EPDM the range of the molar fraction of propylene units 26~
52%.Propylene units content is low, then the tertiary carbon atom on macromolecular chain is few, to the ageing-resistant advantageous of rubber, but if arrives
Lower than 27%, ethylene unit is excessively then likely to form block autohemagglutination, and such block has crystallizing power, can reduce elasticity.Generally
EP rubbers be non-crystalline rubber, glass transition temperature is -58~-50 DEG C.
Based on the studies above background, the present invention provides a kind of preparation methods of the thermally protective materials of lithium ion battery, divide
It is not prepared for adding the EPDM base thermally protective materials of different crosslinking agents and different-thickness, and to this in terms of thermal protective performance
Material has carried out comprehensive test assessment, and then has carried out effective security protection to lithium ion battery.
The safety of electric car and the safety of the core component (lithium ion battery) of its dynamical system are closely bound up.It mentions
The safety of high-lithium ion battery is most important to the safety research of electric car, and reinforces the thermal protection to lithium ion battery
Safety for improving lithium ion battery has the basic meaning of great researching value and reality.
Summary of the invention
Present invention is generally directed to the deficiencies of current lithium ion battery thermal protection technology, provide a kind of for lithium ion battery
Thermally protective materials and preparation method thereof.Contribution of the invention, which first consists in, has selected ethylene propylene diene rubber as lithium ion battery
Thermally protective materials, prevent battery skewered, explosion；The present invention, which further contributes, to be, is introduced in ethylene propylene diene rubber
Boron bakelite resin improves the thermal decomposition performance and anti-flaming thermal-insulation performance of ethylene propylene diene rubber；The present invention further contributes also
It is that the ethylene propylene diene rubber for having selected special ethylene unit content range as rubber base material, further improves ternary
The thermal decomposition performance and anti-flaming thermal-insulation performance of EP rubbers；The other contribution of the present invention also also resides in selection two-(t-butyl peroxy
Change isopropyl) benzene as crosslinking agent reduces pollution and odor dispersion；Contribution of the invention further contribute lie also in it is specific
The selection of fire retardant.
Provided by the present invention for the thermally protective materials of lithium ion battery, raw material composition includes: ethylene propylene diene rubber, tree
Rouge, fiber and auxiliary agent, the auxiliary agent include fire retardant and selected from plasticizer, activator, coupling agent, reinforcing agent, promotor, vulcanization
One of agent etc. is a variety of.
Preferably:
The EPDM is bulk, and acetate unit content is between 45~50%, parts by weight 100；Or
The resin, including boron bakelite resin, parts by weight are 5~45, preferably 10~40 parts by weight；Or
The plasticizer, including atoleine, parts by weight are 1~10, preferably 2~5 parts by weight；Or
The fiber, including PBI fibre (PBI), Poly-p-phenylene benzobisthiazole (PBO), parts by weight are
1~10, preferably 2~8 parts by weight；Or
The activator, including nano zine oxide, parts by weight are 2~15, preferably 4~10 parts by weight；Or including tristearin
Acid, parts by weight are 0.2~5, preferably 0.5~2 parts by weight；Or
The fire retardant can be phosphorus flame retardant, including aluminum diethylphosphinate (ADP), ammonium polyphosphate (APP), weight
Measuring part is 10~65, preferably 15~60 parts by weight；Or it can be silicon-series five-retardant, including cage type octaphenyl silsesquioxane
(OPS), parts by weight are 0.5~10, preferably 1~7 parts by weight；Or
The coupling agent, including silane coupling agent, parts by weight are 0.5~10, preferably 1~5 parts by weight；Or
The reinforcing agent, including white carbon black, parts by weight are 5~60, preferably 10~55 parts by weight；Or including zinc borate,
Parts by weight are 1~15, preferably 2~10 parts by weight；Or
The promotor, including accelerant CZ, parts by weight are 1~10, preferably 2~5 parts by weight；Or including diphenylguanidine,
Parts by weight are 0.2~2, preferably 0.5~1 parts by weight；Or
The crosslinking agent refers to cumyl peroxide, and parts by weight are 1~10, preferably 2~5 parts by weight；Or more preferably
Two-(t-butylperoxyisopropyl) benzene, parts by weight are 1~10, preferably 2~5 parts by weight；Or
The vulcanizing agent refers to sulphur, and parts by weight are 0.2~5, preferably 0.5~2 parts by weight.
The present invention also provides the preparation methods of the thermally protective materials for lithium ion battery, include the following steps:
Step 1, preparation addition fire retardant ternary ethlene propyene rubbercompound material: weigh ethylene propylene diene rubber EPDM, resin,
Crosslinking agent, fiber and auxiliary agent, the auxiliary agent include fire retardant and selected from plasticizer, activator, coupling agent, reinforcing agent, promotor,
One of vulcanizing agent etc. is a variety of, and carrying out the mixing of rubber, (plasticate 10-20min, and vulcanization time is true by vulcameter with vulcanization
It is fixed, using t90As vulcanization time)
The EPDM, acetate unit content is between 45~50%, parts by weight 100.
The resin, including boron bakelite resin, parts by weight are 5~45, preferably 10~40 parts by weight.
The plasticizer, including atoleine, parts by weight are 1~10, preferably 2~5 parts by weight.
The fiber, including PBI fibre (PBI), Poly-p-phenylene benzobisthiazole (PBO), parts by weight are
1~10, preferably 2~8 parts by weight.
The activator, including nano zine oxide, parts by weight are 2~15, preferably 4~10 parts by weight；Or including tristearin
Acid, parts by weight are 0.2~5, preferably 0.5~2 parts by weight.
The fire retardant can be phosphorus flame retardant, including aluminum diethylphosphinate (ADP), ammonium polyphosphate (APP), weight
Measuring part is 10~65, preferably 15~60 parts by weight；Or it can be silicon-series five-retardant, including cage type octaphenyl silsesquioxane
(OPS), parts by weight are 0.5~10, preferably 1~7 parts by weight.
The coupling agent, including silane coupling agent, parts by weight are 0.5~10, preferably 1~5 parts by weight.
The reinforcing agent, including white carbon black, parts by weight are 5~60, preferably 10~55 parts by weight；Or including zinc borate,
Parts by weight are 1~15, preferably 2~10 parts by weight.
The promotor, including accelerant CZ, parts by weight are 1~10, preferably 2~5 parts by weight；Or including diphenylguanidine,
Parts by weight are 0.2~2, preferably 0.5~1 parts by weight.
The crosslinking agent refers to cumyl peroxide, and parts by weight are 1~10, preferably 2~5 parts by weight；Or two-(tertiary fourth
Base isopropyl peroxide) benzene, parts by weight are 1~10, preferably 2~5 parts by weight.
The vulcanizing agent refers to sulphur, and parts by weight are 0.2~5, preferably 0.5~2 parts by weight.
Step 2, the roller spacing for adjusting double roll mill, are set as 3-6mm for finished product thickness.Sample need to be made in advance to half
Finished product (size for example can be 100mm × 100mm according to battery needs), is vulcanized again after parking 8h or more.Sample is most
Good curing temperature is 150-180 DEG C, such as 160 DEG C.The pressure of vulcanizer is set as 10-15MPa.
The present invention also provides the purposes that the thermally protective materials are used to prevent battery skewered, explosion.
Also the performance of gained thermally protective materials is tested in the application, specifically includes following test:
Beginning thermal decomposition temperature and residual qualities: using the TG209F1 type thermal gravimetric analyzer of Nai Chi company of Germany to step 1
It is tested with EPDM obtained by step 2, measures it and originate thermal decomposition temperature and residual qualities.Temperature test section is 40 DEG C
~900 DEG C, heating rate is 10 DEG C/min.
Back temperature test: warm test equipment is carried on the back using Beijing Institute of Technology's self-control, respectively to step at 500 DEG C, 800 DEG C
Rapid 1 and step 2 obtained by EPDM carry out back temperature test.Using liquefied petroleum gas as incendiary source, straight fire is vertical to burn sample just
Face carries out real-time monitoring to sample back temperature by 2 thermocouples directly contacted with the sample back side；Experimental result takes it flat
Mean value, temperature acquisition time interval is 2s, and is recorded by test software to data.Sample having a size of 100mm × 100mm ×
Two kinds of samples of 3mm and 100mm × 100mm × 6mm.
Gas composition analysis: the EPDM for adding different crosslinking agents is tested using gas chromatography-mass spectrometry, is tied
Close obtained spectrogram and software analysis result concrete analysis gas componant.Furnace temperature is set as 200 DEG C, and split ratio is set as 50:1,
Using helium as protection gas.
Thermal protection test: 5 pieces of ter-polymers lithium batteries are bundled into together, and each ter-polymers lithium battery it
Between place 3mm thickness ethylene-propylene-diene monomer film, therebetween by iron wire winding, High temperature-resistanadhesive adhesive tape fixation in a manner of link together,
Medium position between every piece of battery places thermocouple.Then it using methane as incendiary source, ignites in the middle part of first piece of battery, together
When timing start, and to the fire-resistance behavior in lithium ion battery combustion testing carried out shooting record, to detect flame
When spreading to the 5th piece of battery by first piece of battery, the flame temperature of each point changes with time trend, probes into each battery
Fire-resistance behavior, while explosive fire accident behavior is specifically investigated with high-speed photography equipment, to sum up EPDM base thermal protection
Rule is tested in thermal protection of the material under lithium ion battery superheat state.
This method the utility model has the advantages that
EPDM base thermally protective materials prepared by the present invention significantly improve lithium ion battery under the combustion case that happens suddenly
Thermal protective performance, by control temperature field, the periphery surface temperature of adjacent, similar lithium ion battery is reduced, to drop
The probability of low its burning and explosion；Further preferred effect can also reduce pollution, improve smell of burning.
Detailed description of the invention
Fig. 1 is to carry on the back warm experimental apparatus for testing figure.
Fig. 2 is the ethylene propylene diene rubber thermally protective materials for carry on the back temperature test.
Fig. 3 is the GCMS test curve that the EPDM of cumyl peroxide is added in embodiment 1.
Fig. 4 is the GCMS test curve that the EPDM of two-(t-butylperoxyisopropyl) benzene is added in embodiment 2.
Fig. 5 is the ter-polymers lithium battery burning sprawling rule in embodiment 1 with ethylene-propylene-diene monomer film thermally protective materials
Restrain Experimental equipment.
Fig. 6 is the ter-polymers lithium battery group integral combustion in embodiment 1 with ethylene-propylene-diene monomer film thermally protective materials
Fact figure.
Fig. 7 is the ter-polymers lithium battery group combustion explosion in embodiment 4 with ethylene-propylene-diene monomer film thermally protective materials
Battery exterior appearance figure after test.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention is described in more detail.
Embodiment 1
The EPDM of 100g is plasticated 15min on the double roll mill first, 5g atoleine, 8g fiber are added later, under
Piece it is thin it is logical several times, wait estimate above-mentioned filler dispersion it is more uniform after sequentially add 5g nano zine oxide, 1g stearic acid, 4g zinc borate,
The fillers such as 20gADP, 5gOPS, 5g silane coupling agent, 20g white carbon black, be eventually adding 20g boron bakelite resin, 2g accelerant CZ,
0.5g diphenylguanidine, 4g cumyl peroxide and 0.8g sulphur, thin logical bottom sheet several times.
Sample thickness is respectively set as 3mm and 6mm, parks 8h or more, then as requested in a particular mold in 160
DEG C, vulcanize in 15MPa vulcanizing press final sample be made by test request after a certain period of time.Vulcanization time is vulcanized by no rotor
Instrument determines, using t90 as vulcanization time.Wherein 3mm thickness sample vulcanization time is 1620s, and 6mm thickness sample vulcanization time is
1740s。
Performance test 1
The EPDM for taking 0.1g addition cumyl peroxide, using the TG209F1 type thermogravimetic analysis (TGA) of German Nai Chi company
Instrument tests it, measures it and originates thermal decomposition temperature and residual qualities.Temperature test section is 40 DEG C~900 DEG C, heating
Rate is 10 DEG C/min.As a result are as follows: temperature when thermal weight loss reaches 5% is 237 DEG C, maximum heat weight loss rate be 15.04 (%/
Min), it is 28.44% that corresponding temperature, which is the residual substance quality at 464 DEG C, 900 DEG C, when maximum heat weight loss rate.
Performance test 2
Fire source temperature be 500 DEG C, 800 DEG C under conditions of, to different-thickness addition cumyl peroxide EPDM into
The test of row back temperature, sample size is respectively 100mm × 100mm × 3mm and 100mm × 100mm × 6mm.It as a result is 500 DEG C
The equilibrium temperature of the sample of lower 3mm is 354 DEG C, and stablizing the time is 706s, and the equilibrium temperature of 6mm sample is 290 DEG C, stablizes the time
For 1305s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is 373 DEG C, and stablizing the time is 1132s.
Performance test 3
It is tested using EPDM of the gas chromatography-mass spectrometry to addition cumyl peroxide, in conjunction with obtained spectrum
Figure and software analysis result make a concrete analysis of gas componant.Furnace temperature is set as 200 DEG C, and split ratio is set as 50:1, is made using helium
To protect gas.Test result shows that major cleavage products have 8 kinds.
Performance test 4
From the point of view of battery entirety intensity of a fire situation, first piece of battery of calcination is continued with 600 DEG C of Vertical Flame and is kept
50min, in the process, only first piece of battery explosion, with first piece of battery be in close contact ethylene propylene diene rubber be in
Reveal and burns into charcoal state, and other batteries and ethylene propylene diene rubber intimate contact with it are not ignited.8s after igniting, the
One piece is ignited；When 30s, first piece of battery explosion；Between 31s-8min04s, battery continues with larger flame combustion
Flame is gradually reduced after a period of time；When to 8min05s, fray-out of flame.
From the point of view of battery front side (left side), anti-(right side) face combustion case, first piece of battery belong to open fire calcination cause it is quick-fried,
Remaining battery belongs to heat baking and does not cause quick-fried.When first piece of battery is burnt by straight fiery calcination, a large amount of heat transfer is gone down, but
Due to the presence of ethylene propylene diene rubber heat-insulating material, so that the intensity of a fire and not up to remaining battery and ternary second intimate contact with it
Third rubber；Though some heat transfer is to remaining four pieces of battery, heat is less, does not make its explosion, illustrates first piece
Ethylene propylene diene rubber heat-insulating material plays the role of being effectively protected.
Embodiment 2
This embodiment differs from embodiment 1 in that crosslinking agent is chosen to be two-(t-butylperoxyisopropyl) benzene,
Wherein 3mm thickness sample vulcanization time be 1860s, 6mm thickness sample vulcanization time be 2160s, rest part with 1 phase of embodiment
Together.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 242 DEG C, and maximum heat weight loss rate is 14.33
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 462 DEG C, 900 DEG C was 28.21%.
Performance test 2
Back temperature result is that the equilibrium temperature of the sample of 3mm at 500 DEG C is 346 DEG C, and stablizing the time is 448s, 6mm sample
The equilibrium temperature of product is 316 DEG C, and stablizing the time is 1118s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is
396 DEG C, stablizing the time is 1098s.
Performance test 3
Show that major cleavage products there are 5 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
As a result there was only first piece of battery explosion, the ethylene propylene diene rubber being in close contact with first piece of battery shows combustion
It chars state, and other batteries and ethylene propylene diene rubber intimate contact with it are not ignited.10s after igniting, first piece
It is ignited；When 34s, first piece of battery explosion；Between 35s-7min28s, battery continues with one section of larger flame combustion
Flame is gradually reduced after time；When to 7min29s, fray-out of flame.
Embodiment 3
This embodiment differs from embodiment 1 in that not adding boron bakelite resin, wherein 3mm thickness sample vulcanization time is
1560s, 6mm thickness sample vulcanization time are 1800s, and rest part is same as Example 1.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 152 DEG C, and maximum heat weight loss rate is 21.56
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 313 DEG C, 900 DEG C was 17.32%.
Performance test 2
Back temperature result is that the sample of 3mm at 500 DEG C is burnt, and the equilibrium temperature of 6mm sample is 348 DEG C, when stablizing
Between be 869s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is 423 DEG C, and stablizing the time is 674s.
Performance test 3
Show that major cleavage products there are 8 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
First piece, second piece, third block, the 4th piece of battery explode, the ternary second between the battery to explode
Third rubber, which shows, burns into charcoal state, and the 5th piece of battery and ethylene propylene diene rubber intimate contact with it are not ignited.
9s after igniting, first piece is ignited；When 32s, first piece of battery explosion；Second piece of battery explosion when 1min15s；
Third block battery explosion when 2min08s；4th piece of battery explosion when 2min53s；Between 33s-29min54s, battery continue with
Rear flame is gradually reduced larger flame combustion for a period of time；When to 29min55s, fray-out of flame.
Embodiment 4
This embodiment differs from embodiment 1 in that fire retardant ADP is substituted for aluminium hydroxide, wherein 3mm thickness sample
Vulcanization time is 1680s, and 6mm thickness sample vulcanization time is 1980s, and rest part is same as Example 1.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 198 DEG C, and maximum heat weight loss rate is 17.29
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 381 DEG C, 900 DEG C was 21.69%.
Performance test 2
Back temperature result is that the equilibrium temperature of the sample of 3mm at 500 DEG C is 367 DEG C, and stablizing the time is 402s, 6mm sample
The equilibrium temperature of product is 335 DEG C, and stablizing the time is 737s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is
348 DEG C, stablizing the time is 968s.
Performance test 3
Show that major cleavage products there are 8 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
First piece, second piece of battery explode, the ethylene propylene diene rubber between battery to explode shows combustion
It chars state, and its excess-three block battery and ethylene propylene diene rubber intimate contact with it are not ignited.7s after igniting, first
Block is ignited；When 29s, first piece of battery explosion；Second piece of battery explosion when 1min07s；Between 30s-16min45s,
With larger flame combustion, rear flame is gradually reduced for a period of time for battery continuation；When to 16min46s, fray-out of flame.
Embodiment 5
This embodiment differs from embodiment 1 in that fire retardant OPS is replaced APP, wherein 3mm thickness sample vulcanization time
For 1920s, 6mm thickness sample vulcanization time is 2220s, and rest part is same as Example 1.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 229 DEG C, and maximum heat weight loss rate is 16.96
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 407 DEG C, 900 DEG C was 25.93%.
Performance test 2
Back temperature result is that the equilibrium temperature of the sample of 3mm at 500 DEG C is 361 DEG C, and stablizing the time is 693s, 6mm sample
The equilibrium temperature of product is 329 DEG C, and stablizing the time is 1148s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is
386 DEG C, stablizing the time is 1059s.
Performance test 3
Show that major cleavage products there are 8 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
First piece, second piece of battery explode, the ethylene propylene diene rubber between battery to explode shows combustion
It chars state, and its excess-three block battery and ethylene propylene diene rubber intimate contact with it are not ignited.8s after igniting, first
Block is ignited；When 31s, first piece of battery explosion；Second piece of battery explosion when 1min14s；Between 32s-18min29s,
With larger flame combustion, rear flame is gradually reduced for a period of time for battery continuation；When to 18min30s, fray-out of flame.
Embodiment 6
This embodiment differs from embodiment 1 in that wherein 3mm thickness sample vulcanizes using the EPDM of 65% ethylene contents
Time is 1800s, and 6mm thickness sample vulcanization time is 1980s, and rest part is same as Example 1.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 208 DEG C, and maximum heat weight loss rate is 19.56
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 407 DEG C, 900 DEG C was 23.32%.
Performance test 2
Back temperature result is that the equilibrium temperature of the sample of 3mm at 500 DEG C is 372 DEG C, and stablizing the time is 681s, 6mm sample
The equilibrium temperature of product is 317 DEG C, and stablizing the time is 1176s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is
394 DEG C, stablizing the time is 1018s.
Performance test 3
Show that major cleavage products there are 8 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
First piece, second piece of battery explode, the ethylene propylene diene rubber between battery to explode shows combustion
It chars state, and its excess-three block battery and ethylene propylene diene rubber intimate contact with it are not ignited.9s after igniting, first
Block is ignited；When 27s, first piece of battery explosion；Second piece of battery explosion when 1min02s；Between 28s-1min03s,
With larger flame combustion, rear flame is gradually reduced for a period of time for battery continuation；When to 17min21s, fray-out of flame.
Embodiment 7
This embodiment differs from embodiment 1 in that using the boron bakelite resin of 30 mass parts, wherein 3mm thickness sample sulphur
The change time is 1680s, and 6mm thickness sample vulcanization time is 1920s, and rest part is same as Example 1.
Performance test 1
Thermal weight loss test result are as follows: temperature when thermal weight loss reaches 5% is 228 DEG C, and maximum heat weight loss rate is 17.42
(%/min), when maximum heat weight loss rate, corresponding temperature be residual substance quality at 436 DEG C, 900 DEG C was 25.73%.
Performance test 2
Back temperature result is that the equilibrium temperature of the sample of 3mm at 500 DEG C is 369 DEG C, and stablizing the time is 673s, 6mm sample
The equilibrium temperature of product is 312 DEG C, and stablizing the time is 1256s；3mm sample is burnt at 800 DEG C, and the equilibrium temperature of 6mm sample is
403 DEG C, stablizing the time is 1079s.
Performance test 3
Show that major cleavage products there are 8 kinds using gas chromatography-mass spectrometry test result.
Performance test 4
First piece, second piece of battery explode, the ethylene propylene diene rubber between battery to explode shows combustion
It chars state, and its excess-three block battery and ethylene propylene diene rubber intimate contact with it are not ignited.10s after igniting, the
One piece is ignited；When 33s, first piece of battery explosion；Second piece of battery explosion when 1min16s；34s-1min17s it
Between, with larger flame combustion, rear flame is gradually reduced for a period of time for battery continuation；When to 17min36s, fray-out of flame.
Comparative example 1
The ter-polymers lithium battery for directly not carrying out ethylene propylene diene rubber thermal protection to 5 pieces carries out combustion explosion test.
Five pieces of batteries explode as the result is shown.10s after igniting, first piece is ignited；When 27s, first piece of battery hair
Raw explosion；Second piece of battery explosion when 59s；When 1min17s, third block battery explosion；The 4th piece of battery is quick-fried when 1min46s
It is fried；When 2min06s, the 5th piece of battery explosion；Between 28s-46min17s, battery continues with one section of larger flame combustion
Flame is gradually reduced after time；When to 46min18s, fray-out of flame.
From above-described embodiment as can be seen that the protective that embodiment 1 and embodiment 2 test lithium ion battery combustion explosion
Can be optimal, and addition cumyl peroxide and two-(t-butylperoxyisopropyl) benzene influence not the heat-proof quality of EPDM
Greatly, but two-(t-butylperoxyisopropyl) benzene are added the smell and organic volatile product assay of EPDM can be significantly reduced, from
And improve practicability of the EPDM in lithium ion battery thermally protective materials.The interaction of human and environment is considered in practical applications
Factor, preferably the EPDM of two-(t-butylperoxyisopropyl) benzene of addition is as lithium ion battery thermally protective materials.
Above-described specific embodiment, presently preferred embodiments of the present invention, the present invention should not be limited to the reality
Apply a disclosure of that.It is all not depart from the lower equivalent or modification completed of spirit disclosed in this invention, both fall within the present invention
The range of protection.
Claims (8)
1. a kind of thermally protective materials of lithium ion battery, raw material composition includes: ethylene propylene diene rubber, resin, fiber and auxiliary agent,
The auxiliary agent include fire retardant and selected from one of plasticizer, activator, coupling agent, reinforcing agent, promotor, vulcanizing agent etc. or
It is a variety of.
2. thermally protective materials described in claim 1, wherein the fire retardant, can be phosphorus flame retardant, including diethyl
Phosphonic acids aluminium (ADP), ammonium polyphosphate (APP), parts by weight are 10~65, preferably 15~60 parts by weight；Or to can be silicon systems fire-retardant
Agent, including cage type octaphenyl silsesquioxane (OPS), parts by weight are 0.5~10, preferably 1~7 parts by weight.
3. thermally protective materials described in claim 1, wherein the EPDM is bulk, acetate unit content 45~50% it
Between, parts by weight 100.
4. thermally protective materials described in claim 1, wherein the resin, including boron bakelite resin, parts by weight are 5~45, excellent
Select 10~40 parts by weight.
5. thermally protective materials described in claim 1, wherein the crosslinking agent, referring to cumyl peroxide, parts by weight are 1~
10, preferably 2~5 parts by weight；Or more preferable two-(t-butylperoxyisopropyl) benzene, parts by weight are 1~10, preferably 2~5
Parts by weight.
6. thermally protective materials described in claim 1, wherein
The plasticizer, including atoleine, parts by weight are 1~10, preferably 2~5 parts by weight；Or
The fiber, including PBI fibre (PBI), Poly-p-phenylene benzobisthiazole (PBO), parts by weight be 1~
10, preferably 2~8 parts by weight；Or
The activator, including nano zine oxide, parts by weight are 2~15, preferably 4~10 parts by weight；Or including stearic acid, weight
Measuring part is 0.2~5, preferably 0.5~2 parts by weight；Or
The coupling agent, including silane coupling agent, parts by weight are 0.5~10, preferably 1~5 parts by weight；Or
The reinforcing agent, including white carbon black, parts by weight are 5~60, preferably 10~55 parts by weight；Or including zinc borate, weight
Part is 1~15, preferably 2~10 parts by weight；Or
The promotor, including accelerant CZ, parts by weight are 1~10, preferably 2~5 parts by weight；Or including diphenylguanidine, weight
Part is 0.2~2, preferably 0.5~1 parts by weight；Or
The vulcanizing agent refers to sulphur, and parts by weight are 0.2~5, preferably 0.5~2 parts by weight.
7. the preparation method of any one of the claim 1-6 thermally protective materials, includes the following steps:
The ternary ethlene propyene rubbercompound material of step 1, preparation addition fire retardant: ethylene propylene diene rubber EPDM, resin, crosslinking are weighed
Agent, fiber and auxiliary agent, the auxiliary agent include fire retardant and selected from plasticizer, activator, coupling agent, reinforcing agent, promotor, vulcanization
One of agent etc. is a variety of, carries out the mixing and vulcanization of rubber；
Finished product thickness is set as 3-6mm thickness by step 2, the roller spacing for adjusting double roll mill, sample need to be made in advance half at
Product are vulcanized again after parking 8h or more, and curing temperature is 150-180 DEG C, and the pressure of vulcanizer is set as 10-15MPa.
8. the purposes that any one of the claim 1-7 thermally protective materials are used to prevent battery skewered, explosion.
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