CN104201312A - Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery - Google Patents
Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery Download PDFInfo
- Publication number
- CN104201312A CN104201312A CN201410413433.XA CN201410413433A CN104201312A CN 104201312 A CN104201312 A CN 104201312A CN 201410413433 A CN201410413433 A CN 201410413433A CN 104201312 A CN104201312 A CN 104201312A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- barrier film
- lithium ion
- ion battery
- power lithium
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a high-fusing-temperature polyethylene membrane applied to a high-power lithium ion battery. The polyethylene membrane is of a sandwich structure, wherein polyethylene microporous membranes crosslinked by electron beam radiation are arranged in an upper layer and a lower layer; an uncross-linked polyethylene microporous membrane is arranged in a middle layer; by virtue of moderately-crosslinked polyethylene microporous membranes, the membrane is high in fusing temperature, low in heat shrinkable performance and stable in high-temperature mechanical performance; by virtue of uncross-linked polyethylene microporous membrane in the middle, the membrane is proper in pore-closing temperature; the polyethylene microporous membranes at the layers are good in compatibility, so that the interlayer adhesive strength is improved, and thus the membrane is excellent in resistance to high-temperature electrolytic corrosion; the membrane is low in cost, simple in process and stable in performance.
Description
Technical field
The present invention relates to a kind of high-power lithium ion battery polyethylene barrier film and preparation method thereof.
Background technology
Lithium ion battery, because having the advantages such as high-energy-density, long circulation life, low self-discharge rate, high open circuit voltage, heavy metal free pollution and memory-less effect, receives much concern at new energy field.But the environments for use such as high-power charge/discharge, shock are had higher requirement to the barrier film of high-power lithium battery, because in high-power charge/discharge situation, battery can produce amount of heat, in order to ensure high-power lithium ion battery fail safe in use, avoid short circuit, the even danger of blast on fire, high-power lithium ion battery diaphragm must have suitable closed pore temperature, high fusing-off temperature.
Polyethene microporous membrane has suitable closed pore temperature (about 120 DEG C); Good thermal endurance, cold resistance; Chemical stability is good; Mechanical strength is good; Dielectric property are good, and this makes polyethene microporous membrane be widely used as lithium battery diaphragm.But general polyethylene barrier film can shrink at 85 DEG C, 110 DEG C can there is significant distortion.Therefore, in order to meet the requirement of high-power lithium ion battery, people have carried out various modifications and raising to the performance of polyethylene barrier film, as three layers of membrane technique, i.e. and tri-layers of composite diaphragm of PP/PE/PP; Surface recombination ceramic technology, compound by ceramic powder and polyethylene, as nano oxidized aluminum composite membrane of PE/ etc.This composite membrane had both kept the closed pore characteristic of barrier film excellence, had greatly improved again fusing-off temperature and the mechanical behavior under high temperature of barrier film.But, the complicated process of preparation of composite membrane; And because the compatibility between the various components of composite diaphragm is bad, the inharmonious meeting of the performance of expanding with heat and contract with cold causes interface binding intensity decline, the lost of life of barrier film.In use high low temperature variation also can cause each component to be separated, thereby reduces barrier film fusing-off temperature and mechanical behavior under high temperature etc.Although add coupling agent or binding agent can solve to a certain extent the problem of the bad and interface binding intensity of material compatibility, but, add coupling agent or binding agent can cause barrier film electrolyte-resistant corrosive nature at high temperature to weaken, introducing interface resistance increases battery in-fighting, thereby reduces performance, the shortening life-span of barrier film and the usefulness of battery of barrier film.Development preparation technology high power battery barrier film simple, with low cost, stable performance is following development trend.
Summary of the invention
The present invention is directed to the fuse problems such as complex process, mechanical behavior under high temperature be unstable of high-power lithium ion battery barrier film, a kind of polyethylene barrier film that has suitable closed pore temperature, high fusing-off temperature and mechanical behavior under high temperature and stablize, can be used for high-power lithium ion battery is provided.
A further object of the present invention is to provide a kind of preparation method who has suitable closed pore temperature, high fusing-off temperature, mechanical behavior under high temperature and stablize, can be used for the polyethylene barrier film of high-power lithium ion battery.
This barrier film that can be used for high-power lithium ion battery of the present invention is made up of polyvinyl resin, comprises three-layer polyethylene film, forms sandwich structure, and wherein upper and lower two-layer is through crosslinked polyethylene film, and intermediate layer is uncrosslinked polyethene microporous membrane.Upper and lower two-layer crosslinked polyethylene film is given mechanical behavior under high temperature, anti-puncture and the high fusing-off temperature of barrier film excellence; Middle uncrosslinked polyethylene layer is given the closed pore temperature that barrier film is suitable.
High-power lithium ion battery of the present invention comprises the steps: by the preparation method of polyethylene barrier film
1) microporous polyethylene barrier film is carried out to electron radiation is crosslinked obtains appropriately crosslinked polyethylene film;
Irradiation intensity when described crosslinking with radiation is 30～300KGy;
The described crosslinking with radiation time is 5～30 minutes;
The viscosity-average molecular weight of described polyethylene barrier film is 10～5,000,000;
2) polyethylene film step 1) being made is as two-layer up and down, and intermediate layer is that uncrosslinked polyethylene film forms sandwich structure formation composite polyethylene barrier film;
The viscosity-average molecular weight of the described uncrosslinked polyethylene film in intermediate layer is 10～5,000,000;
3) by step 2) the composite polyethylene barrier film that makes processes and obtains a kind of high-power lithium ion battery polyethylene barrier film through operations such as hot calender, annealing, cooling, rolling, trimmings.
Described hot calender process comprises pre-calendering and secondary calender line, utilize two rollers side by side hot calender device realize;
Described pre-rolling temperature is 100～130 DEG C;
Described secondary rolling temperature is 130～180 DEG C;
Described annealing temperature is 90～110 DEG C.
beneficial effect of the present invention:
1) lithium ion battery separator of the present invention adopts polyethylene film, has suitable closed pore temperature, with low cost;
2) lithium ion battery separator of the present invention forms sandwich structure by crosslinked polyethylene film/polyethylene film/crosslinked polyethylene film, crosslinked polyethylene layer is given mechanical behavior under high temperature and the anti-puncture of the high fusing-off temperature of barrier film, excellence, can be used as the barrier film of high-power lithium ion battery;
3) lithium ion battery separator layers of material of the present invention is polyethylene, and compatibility is good, and interlayer adhesion is strong, electrolyte-resistant corrosive nature excellence under the barrier film high temperature after hot-forming, and technique is simple, and the life-span is long.
Brief description of the drawings
Fig. 1 is two rollers used in the present invention hot calender devices side by side, wherein, 1---calendering in advance, 1a---stainless steel rider, 1b---stainless steel rider, 2---secondary calendering, 2a---stainless steel rider, 2b---stainless steel rider, 3---annealing process, 4---wind-up roll.
Embodiment
embodiment 1
By commercial polyethylene (viscosity-average molecular weight 1.05 × 10
4) lithium ion battery separator slowly carries out crosslinking with radiation by high-energy electron accelerator, electron radiation cross-linked dosage is 30KGy, radiation treatment 30 minutes.Using the polyethylene barrier film after crosslinking electron beam irradiation as two-layer up and down, middle double team one deck is without the polyethylene barrier film (viscosity-average molecular weight 1.12 × 10 of cross-linking radiation
6), form sandwich structure.The composite membrane of this sandwich structure, slowly by two groups of rollers hot-press arrangement side by side, is heated with circulating heat conduction oil pair roller in roller, by regulating the thickness of clearance control product barrier film of every group of upper and lower two rollers of roller.The surface temperature of pre-calendering stage roller is 100 DEG C, and the surface temperature of secondary calendering stage roller is 130 DEG C, and polyethylene barrier film is annealed 20 minutes under 90 DEG C of conditions subsequently.Finally cooling, rolling, trimming, obtain having high fusing-off temperature, the polyethylene barrier film of suitable closed pore temperature, mechanical mechanics property excellence.
embodiment 2
By polyethylene (viscosity-average molecular weight 5.74 × 10
6) lithium ion battery separator slowly carries out crosslinking with radiation by high-energy electron accelerator, electron radiation cross-linked dosage is 300KGy, radiation treatment 5 minutes.Using the polyethylene barrier film after crosslinking electron beam irradiation as two-layer up and down, middle double team one deck is without the polyethylene barrier film (viscosity-average molecular weight 1.05 × 10 of cross-linking radiation
4), form sandwich structure.By the composite membrane of this sandwich structure slowly by two groups of rollers hot-press arrangement side by side, in roller with the heating of circulating heat conduction oil pair roller, by regulating the thickness of clearance control product barrier film of every group of upper and lower two rollers of roller.The surface temperature of pre-calendering stage roller is 130 DEG C, and the surface temperature of secondary calendering stage roller is 180 DEG C, and polyethylene barrier film is annealed 20 minutes under 110 DEG C of conditions subsequently.Finally cooling, rolling, trimming, obtain having high fusing-off temperature, the polyethylene barrier film of suitable closed pore temperature, mechanical mechanics property excellence.
embodiment 3
By polyethylene (viscosity-average molecular weight 5.09 × 10
5) lithium ion battery separator slowly carries out crosslinking with radiation by high-energy electron accelerator, electron radiation cross-linked dosage is 120KGy, radiation treatment 10 minutes.Using the polyethylene barrier film after crosslinking electron beam irradiation as two-layer up and down, middle double team one deck is without the polyethylene barrier film (viscosity-average molecular weight 5.09 × 10 of cross-linking radiation
5), form sandwich structure.By the composite membrane of this sandwich structure slowly by two groups of rollers hot-press arrangement side by side, in roller with the heating of circulating heat conduction oil pair roller, by regulating the thickness of clearance control product barrier film of every group of upper and lower two rollers of roller.The surface temperature of pre-calendering stage roller is 110 DEG C, and the surface temperature of secondary calendering stage roller is 150 DEG C, and polyethylene barrier film is annealed 20 minutes under 100 DEG C of conditions subsequently.Finally cooling, rolling, trimming, obtain having high fusing-off temperature, the polyethylene barrier film of suitable closed pore temperature, mechanical mechanics property excellence.
The various embodiments described above sample is tested, comprised fusing-off temperature, closed pore temperature, anti-puncture intensity and thermal contraction performance, result is as shown in table 1.
Closed pore temperature, fusing-off temperature: barrier film, electrolyte, electrode assembling are become to simple and easy battery, be placed in baking oven and slowly heat up, interelectrode resistance variations in test temperature-rise period.Temperature when resistance increases is suddenly the closed pore temperature of barrier film, and temperature when resistance declines suddenly is afterwards the fusing-off temperature of barrier film.
Pierce through strength test: use manual compression tester to test under for 1mm/s condition for 0.6mm and puncture speed at needle type radius, maximum puncture load is to pierce through intensity.
Percent thermal shrinkage: barrier film is cut into 5cm × 5cm size, puts into 130 DEG C of baking ovens, test shrinkage after 1 hour.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Closed pore temperature | 142℃ | 132℃ | 136℃ |
| Fusing-off temperature | 176℃ | 213℃ | 194℃ |
| Pierce through intensity | 8.3N | 13.4 N | 10.7N |
| Percent thermal shrinkage | 1.42% | 0.87% | 1.02% |
Claims (7)
1. a high-power lithium ion battery polyethylene barrier film, is characterized in that this polyethylene barrier film has sandwich structure, and wherein upper and lower two-layer is appropriately crosslinked polyethene microporous membrane, and intermediate layer is uncrosslinked polyethene microporous membrane;
Wherein, described appropriately crosslinked method is electron beam irradiation method;
Described irradiation intensity is 30～300KGy, and the time is 5～30 minutes;
The viscosity-average molecular weight of described polyethylene film is 10～5,000,000.
2. a preparation method for polyethylene barrier film for high-power lithium ion battery, is characterized in that this preparation method comprises the following steps:
1) microporous polyethylene barrier film is carried out to electron beam irradiation and within 5～30 minutes, obtain appropriately crosslinked polyethylene film;
2) polyethylene film step 1) being made is as two-layer up and down, and intermediate layer is that uncrosslinked polyethylene film forms sandwich structure formation composite polyethylene barrier film;
3) by step 2) the composite polyethylene barrier film that makes processes and obtains a kind of high-power lithium ion battery polyethylene barrier film through operations such as hot calender, annealing, cooling, rolling, trimmings.
3. the preparation method of polyethylene barrier film for a kind of high-power lithium ion battery according to claim 2, is characterized in that the viscosity-average molecular weight of described polyethylene film is 10～5,000,000.
4. the preparation method of polyethylene barrier film for a kind of high-power lithium ion battery according to claim 2, the irradiation intensity while it is characterized in that the crosslinking with radiation described in step 1) is 30～300KGy.
5. the preparation method of polyethylene barrier film for a kind of high-power lithium ion battery according to claim 2, is characterized in that the hot calender process described in step 3) comprises pre-calendering and secondary calender line, utilize two rollers side by side hot calender device realize.
6. the preparation method with polyethylene barrier film according to a kind of high-power lithium ion battery described in claim 2 or 5, is characterized in that described pre-rolling temperature is 100～130 DEG C, and secondary rolling temperature is 130～180 DEG C.
7. the preparation method of polyethylene barrier film for a kind of high-power lithium ion battery according to claim 2, is characterized in that the annealing temperature described in step 3) is 90～110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410413433.XA CN104201312A (en) | 2014-08-19 | 2014-08-19 | Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410413433.XA CN104201312A (en) | 2014-08-19 | 2014-08-19 | Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104201312A true CN104201312A (en) | 2014-12-10 |
Family
ID=52086576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410413433.XA Pending CN104201312A (en) | 2014-08-19 | 2014-08-19 | Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104201312A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094284A (en) * | 2021-11-16 | 2022-02-25 | 无锡恩捷新材料科技有限公司 | Novel cross-linked diaphragm and preparation method thereof, battery and electronic equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11213979A (en) * | 1998-01-27 | 1999-08-06 | Sumitomo Bakelite Co Ltd | Separator for battery and battery |
| CN1744348A (en) * | 2004-08-30 | 2006-03-08 | 北京东皋膜技术有限公司 | Composite diaphragm for lithium ion secondary cell and lithium ion secondary cell therewith |
| CN1758463A (en) * | 2004-10-10 | 2006-04-12 | 西安迪纳斯科技有限责任公司 | Compound diaphragm used for lithium-ion secondary battery and lithium-ion secondary battery using the diaphragm |
| US20100155982A1 (en) * | 2004-12-23 | 2010-06-24 | Toray Saehan Inc. | Method of preparing a polyethylene microporous film for a rechargeable battery separator |
-
2014
- 2014-08-19 CN CN201410413433.XA patent/CN104201312A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11213979A (en) * | 1998-01-27 | 1999-08-06 | Sumitomo Bakelite Co Ltd | Separator for battery and battery |
| CN1744348A (en) * | 2004-08-30 | 2006-03-08 | 北京东皋膜技术有限公司 | Composite diaphragm for lithium ion secondary cell and lithium ion secondary cell therewith |
| CN1758463A (en) * | 2004-10-10 | 2006-04-12 | 西安迪纳斯科技有限责任公司 | Compound diaphragm used for lithium-ion secondary battery and lithium-ion secondary battery using the diaphragm |
| US20100155982A1 (en) * | 2004-12-23 | 2010-06-24 | Toray Saehan Inc. | Method of preparing a polyethylene microporous film for a rechargeable battery separator |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094284A (en) * | 2021-11-16 | 2022-02-25 | 无锡恩捷新材料科技有限公司 | Novel cross-linked diaphragm and preparation method thereof, battery and electronic equipment |
| WO2023087735A1 (en) * | 2021-11-16 | 2023-05-25 | 苏州捷力新能源材料有限公司 | Novel cross-linked separator and preparation method thereof, battery, and electronic device |
| CN114094284B (en) * | 2021-11-16 | 2024-05-10 | 苏州捷力新能源材料有限公司 | Novel crosslinked diaphragm, preparation method thereof, battery and electronic equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104241571A (en) | Hydrophilic lithium ion battery membrane | |
| KR102518686B1 (en) | All-solid battery and method for manufacturing the same | |
| CN104140502B (en) | A kind of lithium ion battery separator binding agent, preparation method and use the barrier film of this binding agent | |
| CN102683628B (en) | Coextru-lamination barrier film containing nanometer precrosslinked rubber micro mist and use its lithium ion battery | |
| CN102064301A (en) | Method for manufacturing porous multilayer composite diaphragm for lithium battery and diaphragm | |
| RU2008129678A (en) | METHOD FOR PRODUCING A MEMBRANE ELECTRONIC NODE AND REINFORCED ELECTROLYTIC MEMBRANE IN A FUEL ELEMENT WITH A POLYMER ELECTROLYTE, AND A MEMBRANE ELECTRONIC NODE AND REINFORCED ELECTROMOLOMIC ELECTROMYAN EL | |
| KR20160077968A (en) | Polyolefin Film, the Aluminium pouch film comprising the same, and the Secondary Battery comprising the same | |
| JP2017120790A (en) | Adhesive film for tightly sealing metal terminal portion of electricity storage device | |
| US20140272531A1 (en) | Separator for electrochemical cell with thermally induced self-discharge intrinsic in the construction | |
| CA2937869A1 (en) | Electrode pour systeme de stockage de l'energie electrique avec collecteur comportant une couche conductrice de protection et procede de fabrication correspondant | |
| CN104201312A (en) | Polyethylene membrane applied to high-power lithium ion battery and preparation method of polyethylene membrane applied to high-power lithium ion battery | |
| CN104078717A (en) | Test device for short circuit in battery and triggering method | |
| KR102580441B1 (en) | The Apparatus And The Method For Manufacturing Cell | |
| TW201448338A (en) | Copper foil, anode for lithium ion battery, and lithium ion secondary battery | |
| KR20160071800A (en) | A method for manufacturing a fuel cell membrane electrode assembly with high durability | |
| CN113394514B (en) | Composite diaphragm and preparation method and application thereof | |
| CN104064833A (en) | Method for triggering short circuit in battery | |
| CN110707362A (en) | High-performance lithium battery and preparation method thereof | |
| CN105161749A (en) | Shaping apparatus and method for lithium ion battery | |
| CN102729532B (en) | Multilayer porous membrane and preparation method thereof | |
| CN202333016U (en) | Porous multi-layer battery composite film with heat-resistant resin coating | |
| CN112768844A (en) | Preparation method and application of long-lasting tab | |
| US20210043903A1 (en) | Microporous membranes, battery separators, and methods for making and using the same | |
| JP2013201139A5 (en) | ||
| KR20130081446A (en) | The manufacturing method of aluminium pouch film for the secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141210 |
|
| RJ01 | Rejection of invention patent application after publication |