CN1310352C - A lithium secondary battery isolating film and lithium secondary battery using the same - Google Patents
A lithium secondary battery isolating film and lithium secondary battery using the same Download PDFInfo
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- CN1310352C CN1310352C CNB031396615A CN03139661A CN1310352C CN 1310352 C CN1310352 C CN 1310352C CN B031396615 A CNB031396615 A CN B031396615A CN 03139661 A CN03139661 A CN 03139661A CN 1310352 C CN1310352 C CN 1310352C
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- Prior art keywords
- lithium secondary
- secondary battery
- barrier film
- absorbent material
- molecular sieve
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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 present invention relates to an isolation film of a lithium secondary cell, which at least comprises a layer of a strong water absorption material and a macromolecule composite material, wherein the strong water absorption material is selected as a molecular sieve preferably. The strong water absorption material can completely absorb residual moisture and moisture penetrated by water molecules in the mode of gas penetration when the present invention is used, and prevent the poisoning of the lithium secondary cell or the reaction of lithium metal with water, and accordingly, the service life of the lithium secondary cell is enhanced. In addition, the proper combination of the strong water absorption material and the macromolecule material can increase the mechanical strength of the isolation film, and reduce the electrode interpenetration phenomenon of the lithium secondary cell in rolling program composition or the electrode interpenetration phenomenon which is caused by a lithium metal needle-shaped article after a plurality of times of charge and discharge, and accordingly, the safety of the lithium secondary cell is enhanced. The present invention also relates to the Lithium secondary cell using the isolation film.
Description
[technical field]
The present invention relates to lithium secondary battery, relate in particular to a kind of lithium secondary battery barrier film and use the lithium secondary battery of this barrier film.
[background technology]
Lithium secondary battery has been widely used in the consumption electronic products such as mobile phone, notebook computer because it has good characteristics such as high-energy-density, high electromotive force and low self-discharge.
Described lithium secondary battery comprises lithium metal secondary batteries, lithium ion battery and high-polymer lithium battery.The lithium metal secondary batteries is to be negative material with lithium metal or lithium alloy or lithium-containing compound, with transistion metal compound (as V
6O
13, MoS
2, V
2O
5, TiO
2, MnO
2) as positive active material, anhydrous organic solvent is as electrolyte, the general name that cell reaction can a reversible class battery that carries out; Lithium ion battery is the secondary cell in the technical a kind of novel concept that grows up of lithium metal secondary batteries technology, such battery with material with carbon elements such as Delanium or native graphites as negative pole, with metal oxides such as lithium cobalt, lithium nickel, lithium manganese as positive electrode, with anhydrous organic solvent as electrolyte.High-polymer lithium battery comprises two classes, and a class is that electrode is the lithium ion battery of macromolecular material, and another kind of is that electrolyte is the lithium ion battery of solid-state or colloidal state polymer.
Lithium secondary battery all adopts anhydrous organic solvent or organic polymer as electrolyte, requires inside battery moisture-free, because the lithium metal has high chemical activity, the lithium metal contacts with water violent chemical reaction can take place, and causes battery explosion; In addition, hydrone and electrolyte reaction cause poisoning of lithium secondary battery, reduce the useful life of lithium secondary battery.
Therefore in the manufacturing process of battery, need the airborne relative humidity of strict control less than 0.04% (being Dew point=-56 ℃).Need high cost but control airborne relative humidity less than 0.04%, and still can't avoid residual a certain amount of hydrone in the preparation process.In addition, lithium secondary battery also can't be avoided the hydrone impervious after long-term the use, causes battery functi on forfeiture or battery security problem.
[summary of the invention]
The lithium secondary battery barrier film that the purpose of this invention is to provide a kind of tool strong absorptive.
Another object of the present invention provides a kind of lithium secondary battery that contains above-mentioned barrier film.
The invention provides a kind of lithium secondary battery barrier film, wherein this barrier film comprises the last one absorbent material-polymer composite layer at least, this layer is skeleton with the macromolecular material, strong absorbent material has dew point and is lower than-56 ℃ strong absorptive, particle size range is 10 nanometers～10 micron, be scattered in the macromolecular material, macromolecular material is 1: 4～3: 4 with the weight ratio of strong absorbent material.Strong absorbent material comprises molecular sieve etc., and macromolecular material is an organic polymer
The present invention also provides a kind of lithium secondary battery that contains above-mentioned barrier film.
Barrier film provided by the invention has the following advantages: strong absorbent material is added in the barrier film, can adsorb the residual or moisture that infiltrates when using in the lithium secondary battery processing procedure fully, reduce the cell preparation cost, prevent in the battery use that lithium ion battery is poisoned or the lithium metal secondary batteries in lithium metal and water generation vigorous reaction, thereby the useful life of prolongation lithium secondary battery.In addition, strong absorbent material is entrained in the macromolecular material, can strengthen the barrier film mechanical strength, can reduce electrode in the lithium secondary battery spreading processing procedure and intert phenomenon or repeatedly discharge and recharge electrode that back lithium metal needle-like deposits yields causes and intert phenomenon, thereby improve safety of lithium secondary battery.
[description of drawings]
Fig. 1 is a first embodiment of the invention lithium secondary battery barrier film structural representation.
Fig. 2 is a first embodiment of the invention lithium secondary battery internal structure schematic diagram.
Fig. 3 is a second embodiment of the invention lithium secondary battery barrier film structural representation.
Fig. 4 is a second embodiment of the invention lithium secondary battery internal structure schematic diagram.
Fig. 5 is a third embodiment of the invention lithium secondary battery barrier film structural representation.
Fig. 6 is a third embodiment of the invention lithium secondary battery internal structure schematic diagram.
[embodiment]
As shown in Figure 1, the lithium secondary battery barrier film 124 of first embodiment of the invention comprises the last one absorbent material-polymer composite layer, this layer is a skeleton with macromolecular material 12, strong absorbent material has dew point and is lower than-56 ℃ strong absorptive, particle size range is 10 nanometers～10 micron, be scattered in the macromolecular material, macromolecular material 12 is 1: 4～3: 4 with the weight ratio of strong absorbent material.Strong absorbent material comprises molecular sieve 11, and molecular sieve 11 can be zeolite molecular sieve, carbon molecular sieve, but is not limited thereto, and has strong absorptive and gets final product, and is preferably the 3A molecular sieve.Macromolecular material 12 is an organic polymer, as polyethylene, polypropylene, polymethyl methacrylate, polyvinyl chloride, polyethyleneglycol diacrylate, polyethylene pyrrolidone, polyvinylidene fluoride one or more mixture wherein, but is not limited thereto.
The preparation of lithium secondary battery barrier film 124 of the present invention can be adopted the known method for preparing the lithium secondary battery barrier film of any public.Particularly, the preparation method of this barrier film may further comprise the steps:
Preparation macromolecular material 12 and molecular sieve 11 that barrier film is used at first are provided, and molecular sieve is carried out the physical property miniaturization, make its particle diameter in 10 nanometers～10 micrometer ranges.
Secondly macromolecular material 12 is dissolved in organic solvent.Organic solvent is an acetone, but is not limited thereto.The mass concentration of macromolecular material in solution is 5～40%.
In solution, add molecular sieve 11 then.Macromolecular material 12 is 1: 4～3: 4 with the weight ratio of molecular sieve 11 in solution.This solution becomes even slurry after fully mixed.
Slurry being coated in becomes warm film again on the polyester film substrate.To wet film in 120 ℃ times dry 15 minutes, film is soaked in dry environment takes out after 30 seconds in the electrolyte again, inhale the liquid on striping surface with filter paper.
As shown in the figure, the lithium secondary battery 120 of first embodiment of the invention comprises housing 121, positive pole 122, negative pole 123, organic electrolyte (figure indicates) and barrier film provided by the present invention 124.
Anodal 122 material mainly contains transition metal oxide or sulfide, is preferably lithium manganese, lithium nickel, lithium cobalt or lithium-barium oxide.
Organic electrolyte comprises propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxy-ethane or its mixture.
Lithium secondary battery of the present invention can have Any shape, as cylindric, prism-shaped, sheet or button-type.
The preparation of lithium secondary battery of the present invention can be adopted the known method for preparing lithium secondary battery of any public.Particularly, a kind of method commonly used is included in positive pole 122 and the negative poles of placing in the housing 121 by barrier film 124 couplings 123, subsequently toward wherein injecting electrolyte and with its sealing.The electrolytical method of preferred vacuum injection conduct injection, but it is not had special restriction.Also the electrode 122,123 of coupling can be flooded with electrolyte solution before in placing housing 121.
Second embodiment of the invention provides a kind of lithium secondary battery 220 that has double-deck barrier film 224 and use this double-decker barrier film.Second embodiment and the first embodiment difference are that this barrier film 224 also comprises a low melting point organic polymer layers 13, and this organic polymer layers 13 is formed at a surface of strong absorbent material-polymer composite layer.Organic polymer is preferably polyethylene.
Third embodiment of the invention provides a kind of lithium secondary battery 320 that has the barrier film 324 of three-decker and use this three-decker barrier film.The 3rd embodiment and the first embodiment difference are that barrier film 324 is three-decker, comprise that one deck does not contain the porous low melting point organic polymer films 13 and a pair of strong absorbent material-polymer composite film of strong absorbent material, the porous low melting point organic polymer films 13 that does not contain strong absorbent material is between a pair of strong absorbent material-polymer composite film.Wherein porous low melting point organic polymer films 13 is preferably polyethylene porous membrane, and this perforated membrane melts when the battery serviceability temperature surpasses 110 ℃, blocks the isolation fenestra, turn-offs path between the battery plus-negative plate, prevents internal short-circuit of battery.
For strong absorbent material; the embodiment of the invention all adopts molecular sieve to be described in detail; but it will be appreciated by those skilled in the art that strong absorbent material is not limited to molecular sieve, have the aerosil particles of strong absorptive or material such as alumina powder jointed and all can replace silica gel and be applied in the middle of the present invention.
Barrier film provided by the invention has the following advantages: strong absorbent material makes an addition in the barrier film, can adsorb the residual or moisture that infiltrates when using in the lithium secondary battery processing procedure fully, reduce the cell preparation cost, prevent in the battery use that lithium ion battery is poisoned or the lithium metal secondary batteries in lithium metal and water generation vigorous reaction, thereby the useful life of prolongation lithium secondary battery.In addition, strong absorbent material is doped in the macromolecular material, can strengthen the barrier film mechanical strength, can reduce electrode in the lithium secondary battery spreading processing procedure and intert phenomenon or repeatedly discharge and recharge electrode that back lithium metal needle-like deposits yields causes and intert phenomenon, thereby improve safety of lithium secondary battery.
Claims (8)
1. lithium secondary battery barrier film, it is characterized in that this barrier film comprises the last one absorbent material-polymer composite layer at least, this layer is skeleton with the macromolecular material, strong absorbent material is scattered in the macromolecular material, this macromolecular material is one or more a mixture in polyethylene, polypropylene, polyvinyl chloride, polyethyleneglycol diacrylate, the polyethylene pyrrolidone, this strong absorbent material is a molecular sieve, and macromolecular material is 1: 4～3: 4 with the weight ratio of strong absorbent material.
2. lithium secondary battery barrier film as claimed in claim 1 is characterized in that strong absorbent material has dew point and is lower than-56 ℃ strong absorptive.
3. lithium secondary battery barrier film as claimed in claim 4 is characterized in that strong absorbent material particle size range is 10 nanometers～10 micron.
4. lithium secondary battery barrier film as claimed in claim 4 is characterized in that molecular sieve comprises zeolite molecular sieve or carbon molecular sieve.
5. lithium secondary battery barrier film as claimed in claim 4 is characterized in that molecular sieve is preferably the 3A molecular sieve.
6. lithium secondary battery barrier film as claimed in claim 1 is characterized in that one of strong absorbent material-polymer composite layer surface forms a low melting point organic polymer layers.
7. lithium secondary battery barrier film as claimed in claim 1, it is characterized in that this barrier film comprises an a pair of strong absorbent material-polymer composite layer and a low melting point organic polymer layers, the low melting point organic polymer layers is between a pair of strong absorbent material-polymer composite layer.
8. lithium secondary battery, comprise housing and place housing interior positive pole, negative pole, organic electrolyte solution and barrier film, it is characterized in that this barrier film comprises the last one absorbent material-polymer composite layer at least, this macromolecular material is one or more a mixture in polyethylene, polypropylene, polyvinyl chloride, polyethyleneglycol diacrylate, the polyethylene pyrrolidone, this strong absorbent material is a molecular sieve, and macromolecular material is 1: 4～3: 4 with the weight ratio of strong absorbent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031396615A CN1310352C (en) | 2003-06-27 | 2003-06-27 | A lithium secondary battery isolating film and lithium secondary battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031396615A CN1310352C (en) | 2003-06-27 | 2003-06-27 | A lithium secondary battery isolating film and lithium secondary battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1567614A CN1567614A (en) | 2005-01-19 |
| CN1310352C true CN1310352C (en) | 2007-04-11 |
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|---|---|---|---|
| CNB031396615A Expired - Fee Related CN1310352C (en) | 2003-06-27 | 2003-06-27 | A lithium secondary battery isolating film and lithium secondary battery using the same |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306832B (en) * | 2011-08-12 | 2014-06-11 | 上海交通大学 | PEM (polymer electrolyte membrane) containing lithium ions and manufacturing method thereof |
| CN103855427A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof |
| CN103855424A (en) * | 2012-12-07 | 2014-06-11 | 海洋王照明科技股份有限公司 | Modified polyvinyl chloride electrolyte as well as preparation method thereof, lithium ion battery and application lithium ion battery |
| CN103107301B (en) * | 2013-01-17 | 2015-04-08 | 中国科学院金属研究所 | Novel lithium ion battery diaphragm with inorganic coating and preparation method thereof |
| CN106450512A (en) * | 2016-09-29 | 2017-02-22 | 清华大学 | Metal battery with molecular sieve solid electrolyte layer |
| CN116565450A (en) * | 2022-01-27 | 2023-08-08 | 宁德时代新能源科技股份有限公司 | Multilayer composite separator, secondary battery including the same, and electric device |
| CN115133222A (en) * | 2022-06-06 | 2022-09-30 | 西北工业大学 | Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298209A (en) * | 1999-11-10 | 2001-06-06 | 宇部兴产株式会社 | Battery spacing membranes and lithium secondary battery |
| CN1325145A (en) * | 2000-04-10 | 2001-12-05 | 思凯德公司 | Partition board for high-energy charged lithium cells |
| US20020122986A1 (en) * | 2001-03-02 | 2002-09-05 | Labarge William J. | Lithium battery with separator stored lithium |
-
2003
- 2003-06-27 CN CNB031396615A patent/CN1310352C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298209A (en) * | 1999-11-10 | 2001-06-06 | 宇部兴产株式会社 | Battery spacing membranes and lithium secondary battery |
| CN1325145A (en) * | 2000-04-10 | 2001-12-05 | 思凯德公司 | Partition board for high-energy charged lithium cells |
| US20020122986A1 (en) * | 2001-03-02 | 2002-09-05 | Labarge William J. | Lithium battery with separator stored lithium |
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| Publication number | Publication date |
|---|---|
| CN1567614A (en) | 2005-01-19 |
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Granted publication date: 20070411 Termination date: 20170627 |