CN101702428A - Porous polyolefine isolating film - Google Patents
Porous polyolefine isolating film Download PDFInfo
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- CN101702428A CN101702428A CN200910193813A CN200910193813A CN101702428A CN 101702428 A CN101702428 A CN 101702428A CN 200910193813 A CN200910193813 A CN 200910193813A CN 200910193813 A CN200910193813 A CN 200910193813A CN 101702428 A CN101702428 A CN 101702428A
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- isolating film
- porous
- polyolefine isolating
- porous polyolefine
- film
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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 a porous polyolefine isolating film. The thickness of the isolating film is 35-80 mu m, the porosity is 30-70 percent, the air permeability is 100-1,000 second/100ml and the average pore opening diameter is 0.001-1mu m. By using a lithium ion power battery of the porous polyolefine isolating film, the highest temperatures of a drift bolt and a thermal simulation are all not less than 100 DEG C, and the invention has favorable safety performance, circulating performance and charge-discharge performances.
Description
Technical field
The present invention relates to a kind of lithium ion battery barrier film, especially a kind of porous polyolefine isolating film.
Background technology
As isolated material, porous polyolefin membrane can be widely used in separation, select to see through various materials.For example, porous polyolefin membrane can be used as the separator in secondary filter film, the battery, the separator in the capacitor, and the mother metal of various functional membranes.
Porous polyolefin membrane is fit to be used as the barrier film of lithium ion battery because it not only has high osmosis, and at a certain temperature the melting polymer, stop up intercommunicating pore, thereby cut off electric current to guarantee the safe handling of lithium ion battery." cut-out " is meant that the hole of porous polyolefin membrane is melted resin and stops up, with the resistance of increase film and flowing of interception lithium ion.Collateral security safety wishes that trip temperature is low as far as possible.
In addition, barrier film is the also essential shape that keeps film after hole plug, isolates to guarantee the insulation between the electrode.After if barrier film is cut off the electricity supply, the temperature of lithium ion battery further raises, and the fluidization meeting of barrier film causes that resistance reduces, thereby causes electric current to recover.This temperature is the short circuit temperature, wishes that generally the short circuit temperature is higher.
In recent years, along with the reinforcement of global environmental protection activity, consider that from the angle of conserve energy and resource auto industry is just actively introduced electric automobile.But, because battery needs radiations heat energy for a long time after being cut off, can under abnormal conditions, produce more hotly so have the batteries of electric automobile of higher-energy, may cause battery temperature to be increased to high level or long term maintenance at short notice in the condition of high temperature.At this moment, barrier film might shrink or break and may cause short circuit between the both positive and negative polarity, produces more heats, has had a strong impact on the security performance of battery.
In view of this, necessary provide a kind of have good safety can porous polyolefine isolating film, to realize lower cut-out temperature that batteries of electric automobile is expected and the short circuit temperature of Geng Gao, ensure the safe handling of battery.
Summary of the invention
The objective of the invention is to: a kind of porous polyolefine isolating film with good safety energy is provided.
In order to realize the foregoing invention purpose, the invention provides a kind of porous polyolefine isolating film, the thickness of porous polyolefine isolating film is 35-80 μ m, porosity is 30-70%.
With respect to prior art, porous polyolefine isolating film of the present invention has following technique effect:
At first, porous polyolefine isolating film of the present invention can be applicable in the lithium-ion-power cell, especially in the used for electric vehicle lithium-ion-power cell, because barrier film thickness increases, reduced lithium-ion-power cell generation internal short-circuit greatly, particularly the risk of the internal short-circuit that causes because of the cathode aluminum foil burr.
Secondly, even when short circuit current flow takes place between internal short-circuit, the positive/negative plate, porous polyolefine isolating film of the present invention can increase electronics and ionic polarization, reduces short circuit current and reduces the heat that generates, and reduces the possibility of catching fire and exploding.When adopting porous polyolefine isolating film of the present invention, the maximum temperaturerise during by thermal simulation lithium ion drift bolt is 102 ℃, and actual test result is 98 ℃; When adopting common barrier film, the maximum temperaturerise during by thermal simulation lithium ion drift bolt is 135 ℃, and actual test result is 140 ℃.
At last, porous polyolefine isolating film of the present invention also has excellent cycle performance and charge-discharge performance.
As a kind of improvement of porous polyolefine isolating film of the present invention, the thickness of described porous polyolefine isolating film is 35-50 μ m, and porosity is 30-50%.
As a kind of improvement of porous polyolefine isolating film of the present invention, the thickness of described porous polyolefine isolating film is 40 μ m, and porosity is 40%.
As a kind of improvement of porous polyolefine isolating film of the present invention, the air permeability of described porous polyolefine isolating film is 100-1000 second/100ml, and average opening diameter is 0.001-1 μ m.
As a kind of improvement of porous polyolefine isolating film of the present invention, described barrier film contains the porous polyolefin matrix, and the porous polyolefin matrix is that mean molecule quantity is not less than 1 * 10
5Independent polyolefin, or be not less than 1 * 10 for mean molecule quantity
5, porosity is the polyolefinic mixture of 30-95%.
As a kind of improvement of porous polyolefine isolating film of the present invention, it is 1 * 10 that described polyolefin blend contains mean molecule quantity
6-15 * 10
6Extrahigh-molecular weight polyolefins and mean molecule quantity be 1 * 10
5-1 * 10
6High molecular polyolefine.
As a kind of improvement of porous polyolefine isolating film of the present invention, the trip temperature of described porous polyolefine isolating film is no more than 135 ℃.
As a kind of improvement of porous polyolefine isolating film of the present invention, the short circuit temperature of described porous polyolefine isolating film is not less than 165 ℃.
Embodiment
Below in conjunction with each specific embodiment and comparative example, describe porous polyolefine isolating film of the present invention and its useful technique effect in detail.
Embodiment 1
1) preparation of barrier film
To contain polyolefin blend and plasticizer (as the paraffin) mixer kneader of polyethylene B of polyethylene A, the 95-5% of percentage by weight 5-95%, wherein, the mean molecule quantity of polyethylene A is 2 * 10
6, the mean molecule quantity of polyethylene B is 1 * 10
5-2 * 10
5To mediate product and extrude and make gluey sheet and cooling and solidify, the gluey sheet that will obtain then stretches, and dryness finalization makes porous polyolefine isolating film of the present invention.The thickness of barrier film is 35-80 μ m, and preferred 35-50 μ m is preferably 40 μ m; The porosity of barrier film is 30-70%, and preferred 30-50% is preferably 40%; Air permeability is 1000 seconds/100ml, and average opening diameter is 0.001-1 μ m, is preferably 0.03 μ m.The trip temperature that test records embodiment 1 barrier film is 125 ℃, and the short circuit temperature is 185 ℃.
Need to prove that barrier film also can contain other porous polyolefin matrixes, polyolefin substrate is that mean molecule quantity is not less than 1 * 10
5Independent polyolefin, or be not less than 1 * 10 for mean molecule quantity
5, porosity is the polyolefinic mixture of 30-95%, wherein, it is 1 * 10 that polyolefin blend contains mean molecule quantity
6-15 * 10
6Extrahigh-molecular weight polyolefins and mean molecule quantity be 1 * 10
5-1 * 10
6High molecular polyolefine.
2) preparation of positive plate
Get percentage by weight and be 94% LiFePO
4, 3% Nano carbon fibers peacekeeping 3% water-soluble binder, add deionized water and also stir, then on coating and the aluminium foil, stay in the coating process that 15mm is monolateral not to apply.Oven dry and continuous rolling are cut at the aluminium foil partial continuous roller of uncoated then, are formed with the square wave type collector of continuous monolateral collector, make positive plate.The width of monolateral collector is 8mm, and spacing is 20mm, highly is 15mm.
3) preparation of negative plate
By weight taking by weighing Delanium and water-soluble adhesive carboxymethyl cellulose (CMC) at 95: 5, add deionized water and stirring evenly on back coating and the Copper Foil, stay in the coating process that 15mm is monolateral not to apply.Oven dry and continuous rolling are cut at the Copper Foil partial continuous roller of uncoated then, are formed with the square wave type collector of continuous monolateral collector, make positive plate.The width of monolateral collector is 8mm, and spacing is 20mm, highly is 15mm.
4) preparation of battery
With the positive and negative plate and the assembling of aforementioned porous polyolefine isolating film of the dried square wave type collector that all distributes, injection ethylene carbonate and diethyl carbonate volume ratio 1: 1 and contain the electrolyte of 1M LiPF6 make lithium-ion-power cell.The assessment result of battery sees Table 1.
Embodiment 2
1) preparation of barrier film
The preparation of barrier film is with embodiment 1, and barrier film is of a size of: 1500mm * 54mm
2) preparation of positive plate
With percentage by weight be respectively 85% LiFePO4,5% carbon black and 5% the graphite mixed grinding, dry premix, make anodal powder.Mixed anodal powder is mixed with the deionized water of the acrylic polymer that contains percentage by weight 5%, make slurry, the viscosity of slurry is between 6000-9000mPaS.In the two sides of tiltedly drawing the aluminium net, 110 ℃ of dry down back roll-ins, forming thickness after roll-in is the positive plate of 200 μ m with slurry coating, and compacted density is 2.2g/cm
3At last, positive plate is reduced by size 700mm * 51mm.
2) preparation of negative plate
With percentage by weight be 93% native graphite and the deionized water of the CMC that contains percentage by weight 2%, 5% butadiene-styrene rubber binding agent is mixed and made into slurry, and slurry viscosity is between 3000-5000mPaS.Slurry all is coated on the two sides of Copper Foil, 120 ℃ of dry down back roll-ins, forms the negative plate of the about 120 μ m of thickness after roll-in, compacted density is 1.6g/cm
3At last, negative plate is reduced by size 740mm * 52mm.
4) preparation of battery
By " negative plate-barrier film-positive plate-barrier film-negative plate-barrier film-positive plate " order with positive/negative plate to folded, be wound into spiral helicine electric core.Electric core is welded the back 90 ℃ of vacuumizes 24 hours through lug, and 15g electrolyte is injected in dry back, and electrolyte is LiPF
6-ethylene carbonate (EC)/dimethyl carbonate (DMC)/propene carbonate (PC), wherein, the volume ratio of EC, DMC, PC is 1: 0.8: 0.2, changes into after the encapsulation and obtains lithium-ion-power cell.The battery assessment result sees Table 1.
Embodiment 3
1) preparation of barrier film
The preparation of barrier film is with embodiment 1.
2) preparation of positive plate
With Li
3V
2(PO
4)
3, conductive agent and binding agent mix all in proportion, is coated on the aluminium foil, compacting after the oven dry is sheared according to certain size, is made into positive plate.
3) preparation of negative plate
With Li4Ti
5O
12, after conductive agent and binding agent mix in proportion, be coated on the Copper Foil, compacting after the oven dry is sheared according to certain size, is made into negative plate.
4) preparation of battery
With positive plate, negative plate and barrier film assembling, inject electrolyte, make lithium-ion-power cell.The battery assessment result sees Table 1.
Comparative example
1) preparation of positive plate
With Li
3V
2(PO
4)
3, conductive agent and binding agent mix all in proportion, is coated on the aluminium foil, compacting after the oven dry is sheared according to certain size, is made into positive plate.
2) preparation of negative plate
With Li
4Ti
5O
12, conductive agent and binding agent mix in proportion, and is coated on the Copper Foil, compacting after the oven dry is sheared according to certain size, is made into negative plate.
3) preparation of battery
With positive plate, negative plate and the assembling of common barrier film, inject electrolyte, make lithium-ion-power cell.The battery assessment result sees Table 1.
Table 1 battery performance assessment result
The drift bolt experiment:
The battery of each embodiment and comparative example is done drift bolt test, analog electrical in-core portion short-circuit conditions.The step of drift bolt is:
(1) with 1.0C electric current constant current charge to 3.65V, constant voltage charge to electric current is reduced to 0.05C then, charging stops;
(2) leave standstill 1 hour, measure open circuit voltage then;
(3) be that the steel nail of 5-8mm vertically passes electric core center with a diameter, and keep more than 1 hour.
The test result of drift bolt experiment sees Table 2.
The test result of table 2 drift bolt experiment
| The drift bolt maximum temperature/℃ | The thermal simulation maximum temperature/℃ | The thermal runaway situation | |
| Embodiment 1 | ??100 | ??102 | Do not have blast, nothing is caught fire, no leakage |
| Embodiment 2 | ??101 | ??100 | Do not have blast, nothing is caught fire, no leakage |
| The drift bolt maximum temperature/℃ | The thermal simulation maximum temperature/℃ | The thermal runaway situation | |
| Embodiment 3 | ??100 | ??100 | Do not have blast, nothing is caught fire, no leakage |
| Comparative example | ??135 | ??40 | Blast, leakage |
The announcement of book and instruction according to the above description, the technical staff of the technical field of the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (10)
1. porous polyolefine isolating film, it is characterized in that: the thickness of described porous polyolefine isolating film is 35-80 μ m, and porosity is 30-70%.
2. porous polyolefine isolating film according to claim 1 is characterized in that: the thickness of described porous polyolefine isolating film is 35-50 μ m, and porosity is 30-50%.
3. porous polyolefine isolating film according to claim 1 is characterized in that: the thickness of described porous polyolefine isolating film is 40 μ m, and porosity is 40%.
4. according to each described porous polyolefine isolating film in the claim 1 to 3, it is characterized in that: the air permeability of described porous polyolefine isolating film is 100-1000 second/100ml, and average opening diameter is 0.001-1 μ m.
5. porous polyolefine isolating film according to claim 1 is characterized in that: described barrier film contains the porous polyolefin matrix, and polyolefin substrate is that mean molecule quantity is not less than 1 * 10
5Independent polyolefin, or be not less than 1 * 10 for mean molecule quantity
5, porosity is the polyolefinic mixture of 30-95%.
6. porous polyolefine isolating film according to claim 5 is characterized in that: it is 1 * 10 that described polyolefin blend contains mean molecule quantity
6-15 * 10
6Extrahigh-molecular weight polyolefins and mean molecule quantity be 1 * 10
5-1 * 10
6High molecular polyolefine.
7. porous polyolefine isolating film according to claim 1 is characterized in that: the trip temperature of described porous polyolefine isolating film is no more than 135 ℃.
8. porous polyolefine isolating film according to claim 1 is characterized in that: the short circuit temperature of described porous polyolefin porous isolating membrane is not less than 165 ℃.
9. lithium-ion-power cell, it comprises: positive plate, negative plate, be interval in the barrier film between the positive/negative plate, and electrolyte, it is characterized in that: described barrier film is each described porous polyolefine isolating film in the claim 1 to 8.
10. lithium-ion-power cell according to claim 9 is characterized in that: the drift bolt maximum temperature of described lithium-ion-power cell and thermal simulation maximum temperature all are not less than 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910193813A CN101702428A (en) | 2009-11-10 | 2009-11-10 | Porous polyolefine isolating film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910193813A CN101702428A (en) | 2009-11-10 | 2009-11-10 | Porous polyolefine isolating film |
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| Publication Number | Publication Date |
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| CN101702428A true CN101702428A (en) | 2010-05-05 |
Family
ID=42157327
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163704A (en) * | 2011-03-24 | 2011-08-24 | 中山国安火炬科技发展有限公司 | Lithium battery diaphragm and production method thereof |
| CN103618055A (en) * | 2013-11-12 | 2014-03-05 | 厦门聚微材料科技有限公司 | Preparation method for polyolefin diaphragm of lithium ion battery |
| CN107369804A (en) * | 2017-08-06 | 2017-11-21 | 长沙小新新能源科技有限公司 | A kind of preparation method of lithium battery security diaphragm material |
| CN108539106A (en) * | 2017-03-03 | 2018-09-14 | 住友化学株式会社 | Nonaqueous electrolytic solution secondary battery spacer |
| US10566594B2 (en) | 2017-03-03 | 2020-02-18 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery separator |
-
2009
- 2009-11-10 CN CN200910193813A patent/CN101702428A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163704A (en) * | 2011-03-24 | 2011-08-24 | 中山国安火炬科技发展有限公司 | Lithium battery diaphragm and production method thereof |
| CN102163704B (en) * | 2011-03-24 | 2013-08-28 | 中山国安火炬科技发展有限公司 | Lithium battery diaphragm and production method thereof |
| CN103618055A (en) * | 2013-11-12 | 2014-03-05 | 厦门聚微材料科技有限公司 | Preparation method for polyolefin diaphragm of lithium ion battery |
| CN108539106A (en) * | 2017-03-03 | 2018-09-14 | 住友化学株式会社 | Nonaqueous electrolytic solution secondary battery spacer |
| US10566594B2 (en) | 2017-03-03 | 2020-02-18 | Sumitomo Chemical Company, Limited | Nonaqueous electrolyte secondary battery separator |
| CN108539106B (en) * | 2017-03-03 | 2020-02-21 | 住友化学株式会社 | Separator for nonaqueous electrolyte secondary battery |
| CN107369804A (en) * | 2017-08-06 | 2017-11-21 | 长沙小新新能源科技有限公司 | A kind of preparation method of lithium battery security diaphragm material |
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Open date: 20100505 |