CN202333014U - Combined diaphragm for battery and battery applying same - Google Patents
Combined diaphragm for battery and battery applying same Download PDFInfo
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- CN202333014U CN202333014U CN2011203306913U CN201120330691U CN202333014U CN 202333014 U CN202333014 U CN 202333014U CN 2011203306913 U CN2011203306913 U CN 2011203306913U CN 201120330691 U CN201120330691 U CN 201120330691U CN 202333014 U CN202333014 U CN 202333014U
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- microporous membrane
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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 utility model discloses a battery of battery with combination diaphragm and applied this diaphragm that belongs to various battery with diaphragm technical field. The combined diaphragm is a layer-by-layer combined diaphragm comprising a microporous membrane and a porous membrane, wherein the porous membrane has uniform pore size distribution, and the pore size is 2~3 mu m. The combined diaphragm can be used for zinc-manganese batteries, nickel-zinc batteries, nickel-cadmium batteries, silver-zinc batteries, lead-acid batteries, nickel-hydrogen batteries, lithium ion batteries and fuel batteries. Adopt the utility model provides a battery of combination diaphragm can be used for a plurality of application fields such as cell-phone, notebook computer, audio frequency goods, electric tool, stand-by power supply, vehicle electrical power generating system, has very wide application prospect. The utility model provides a method not only is convenient but also can synthesize the advantage performance of different diaphragms, is favorable to realizing the integrated production of battery, reduces battery manufacturing cost. Adopt the utility model provides a battery of combination diaphragm possesses better normal atmospheric temperature and high temperature cycle performance.
Description
Technical Field
The utility model belongs to the technical field of diaphragm for various batteries, especially diaphragm technical field for lithium ion secondary battery, in particular to battery is with combination diaphragm and applied this diaphragm's battery.
Background
Since the advent of lithium ion batteries in 1990, the development of materials and production techniques for batteries has been rapid, and research on materials for batteries has supported the improvement and improvement of performance of lithium ion batteries, and the all-round improvement of rate capability, high and low temperature performance, safety performance, cycle performance and the like of batteries has led to the rapid popularization of lithium ion batteries in a plurality of application fields such as mobile phones, notebook computers, audio products, electric tools, backup power supplies, vehicle power supply systems and the like. With the expansion of application fields, the lithium ion battery still keeps vigorous market demand in the next decade and is popularized to more application fields.
Separator materials are one of the key materials for lithium ion batteries. The current commercialized diaphragm adopts polyethylene and polypropylene microporous membranes, and the microporous membranes have high porosity, low resistivity, high tensile strength, high acid and alkali resistance, high elasticity and high retention performance on aprotic solvents.
In the conventional art, a single polyolefin separator material is commonly used to fabricate a battery. However, the prior diaphragm material as a whole causes rapid temperature rise when the battery is abused, and the diaphragm can shrink when the temperature exceeds the fusing temperature, so that the positive and negative pole pieces are short-circuited, and further serious safety accidents are caused.
In the battery, along with the continuous operation of the charging and discharging circulation of the battery, the electrolyte is continuously consumed, so that a local electrolyte poor region appears around the negative plate, lithium salt is separated out, a lithium dendrite phenomenon appears, and the diaphragm is further punctured to cause short circuit. Therefore, the electrolyte-enriching capacity of the separator affects the later cycle performance and safety performance of the battery.
At present, with the demand of lithium ion batteries, some new types of microporous separator varieties appear. For example, through electrostatic spinning technology, electron irradiation technology, chemical corrosion technology and the like, the diaphragm has strong superiority in certain aspects, such as high liquid-rich amount, good thermal stability, surface hydrophobicity and the like. However, the mechanical strength of the battery manufactured by the diaphragm is poor, and a micro short circuit phenomenon is easy to occur in the manufacturing process of the battery, so that the product yield is reduced, and the waste of raw materials is further caused.
Disclosure of Invention
In order to solve the problem, the utility model provides a layer upon layer combination technique of comprehensive utilization microporous membrane and porous membrane performance makes it be used for different battery fields as a whole, including fields such as lead-acid battery, nickel-hydrogen battery, lithium ion battery and fuel cell.
The utility model relates to a layer upon layer combination technique of membrane advantage performance in a kind of battery field.
The utility model provides a combined diaphragm for battery, it is the diaphragm that makes up layer upon layer including microporous membrane and porous membrane.
The microporous membrane has safe closed pore temperature, and can effectively cut off current when the temperature of the battery is too high; the porous membrane can not shrink when the temperature in the battery excessively rises, keeps the shape unchanged, effectively separates the positive electrode and the negative electrode, and avoids short circuit.
In this technique, the pore size and morphology of the porous membrane are critical. The most advantageous combination of these is the use of larger pore size porous membranes in this technology, where pores are most preferably through-pores. On the one hand, more electrolyte reserve space can be provided, and on the other hand, the electrolyte reserve space does not have great influence on the migration and transmission of ions. The porous membrane has a uniform pore size distribution. The pore size of the porous membrane is 1~5 μm, preferably 2~3 μm.
The porous membrane has at least one of good thermal stability, high liquid-rich capacity or strong mechanical property, wherein the good thermal stability means that no fusion closed pore appears at more than 150 ℃, the high-temperature shrinkage rate is less than 5 percent, the high liquid-rich capacity means that the porous membrane has the liquid-rich capacity of 1~3 times that of a polyolefin diaphragm, the liquid absorption amount is 120 to 400 percent of the self weight of the diaphragm, and the strong mechanical property means that the tensile strength in the transverse direction and the longitudinal direction is more than 1500Kg/cm 2 。
The microporous membrane is a single-layer microporous membrane or a multi-layer microporous membrane. The microporous membrane can be a single-layer PP, a single-layer PE or a multi-layer PP/PE/PP and other industrialized membrane materials. The microporous membrane has <1 μm and relatively uniform pore size.
The membrane is combined layer by layer, the thickness of the microporous membrane is 20 to 40 mu m, and the thickness of the porous membrane is 5 to 15 mu m.
The porous membrane may be provided on one side of the microporous membrane, or may be provided on both sides of the microporous membrane. The combined diaphragm can adopt a microporous membrane/porous membrane double-layer combination, a microporous membrane/porous membrane/microporous membrane three-layer combination or a porous membrane/microporous membrane three-layer combination and other combinations.
The porous membrane is a single-layer membrane or a multi-layer composite membrane.
The matching property of the combined diaphragm can be divided into a double-layer film system and a multi-layer film system.
The double-layer film system comprises a heat-stable film/high-liquid-rich film, a heat-stable film/strong-chemical-performance film and other combined double-layer film systems.
The multilayer film system comprises a high liquid-rich film/thermal stability film/high liquid-rich film, a high liquid-rich film/thermal stability film/strong chemical performance film, a thermal stability film/high liquid-rich film/strong chemical performance film and other combined multilayer film systems.
The porous membrane is made of organic or inorganic materials and comprises at least one of polyolefin, cellulose and polyester. Among them, preferred is at least one of a polyethylene single-layer film or multilayer film, a polypropylene single-layer film or multilayer film, a hydroxymethylcellulose film, an alkylmethylcellulose film, a polyethylene terephthalate film, a polyvinylidene fluoride-hexafluoropropylene copolymer film, and polytetrafluoroethylene. Further, the organic base material may be added with a composite film of silica, alumina, or the like.
The porous membrane material also comprises a membrane material which is processed by the physical and chemical methods and has special properties of porosity, high adhesiveness, strong electrostatic adsorption, surface hydrophobicity and the like.
The utility model also provides a preparation method of above-mentioned combination diaphragm, combination diaphragm adopt the method of physics to make up and can adopt hot pressing, cold pressing, bond, the combination is accomplished to at least one mode in the electrostatic absorption, and the selection of combination mode should synthesize the physical properties consideration of diaphragm, goes on not influencing the basis that former diaphragm formed. Before physical combination, certain pretreatment work (such as surface electrostatic treatment, preheating and the like) can be carried out.
According to the utility model discloses require, this purpose of layer upon layer combination technique is through the dominant property of certain mode coming comprehensive microporous membrane and porous membrane, on keeping the basis of the good thermal safety control ability of former micropore diaphragm, improves its circulation performance, multiplying power performance, other security performance through the combination with the porous membrane.
The battery system that the battery is suitable for with combination diaphragm is zinc-manganese cell, nickel-zinc battery, nickel-cadmium battery, silver-zinc battery, lead-acid battery, nickel-hydrogen battery, lithium ion battery and fuel cell etc.. Is particularly suitable for lithium ion batteries.
The utility model discloses mainly use lithium ion secondary battery as the example, including positive pole, negative pole, electrolyte and diaphragm. The positive electrode and the negative electrode can be coated by blade coating, extrusion, spraying and the like, and the thickness is adjusted according to the capacity of the battery and the distribution design of a heat flow field.
The lithium ion battery of the utility model is a lithium ion secondary recyclable charge-discharge battery, and the positive active substance of the lithium ion battery can be at least one of lithium cobaltate, lithium manganate, lithium nickelate and ternary materials; the negative active material can be at least one of carbon, stannous oxide and lithium titanate; the diaphragm adopts the utility model provides a combination diaphragm.
The preparation of the positive plate may also involve substances such as dispersing agents, polymer binders, solvents, corrosion inhibitors, conductive agents, and other inorganic fillers.
The negative electrode sheet may also be prepared by using a dispersant, a polymer binder, a solvent, a corrosion inhibitor, a conductive agent, other inorganic fillers and the like.
To achieve the above-mentioned object, the following manner may be adopted:
cutting the positive plate and the negative plate coated on the current collector into required sizes, and drying at a certain temperature, pressure and inert atmosphere. The microporous membrane and the porous membrane material are combined into the required diaphragm material through the modes of electrostatic adsorption, hot pressing, bonding and the like in a certain treatment mode, and the required diaphragm material is dried at a certain temperature, pressure and inert atmosphere. Then, the positive plate, the negative plate and the combined diaphragm are manufactured into a 18650 type battery or an aluminum plastic film packaging battery in a winding or laminating mode.
Adopt the utility model provides a combination diaphragm material, and then assemble into the battery of required type. The utility model provides a method of preparation combination diaphragm is not only convenient but also can synthesize different diaphragm advantage performance, is favorable to realizing the integrated production of battery, reduces battery manufacturing cost. Adopt the utility model provides a battery of combination diaphragm equipment can be used for a plurality of application fields such as cell-phone, notebook computer, audio frequency goods, electric tool, stand-by power supply, vehicle electrical power generating system, has very wide application prospect. The utility model provides a simple, effective, convenient and fast method for improving the overall performance of the current diaphragm system. The utility model provides a battery system that security performance, circulation performance, rate capability are better.
Adopt the utility model provides a battery of combination diaphragm possesses better normal atmospheric temperature and high temperature cycle performance.
Drawings
Fig. 1 is a schematic view of a double-layer combined diaphragm of embodiment 1 of the present invention; wherein 1 is a common microporous membrane layer, 2 is a porous membrane layer, and 3 is the form of pores in the porous layer.
Fig. 2 is a normal temperature cycle performance curve, cycle number and capacity retention rate variation of the lithium ion battery in the combined process and the conventional process in example 1.
FIG. 3 is a plot of the normal temperature cycle performance, cycle number and capacity retention rate of the lithium ion battery of the combined process of example 2 and the conventional process.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Example 1
The combined diaphragm of the embodiment is a double-layer diaphragm system and consists of a microporous diaphragm and a porous diaphragm, wherein the porous diaphragm is arranged on one side of the microporous diaphragm. The microporous membrane is a polypropylene microporous membrane, the thickness is 20 to 30 micrometers, and the pore size is 0.2 to 0.5 micrometer; the porous membrane is made of polyester membrane with high liquid absorption, the liquid absorption is 200% of the self weight of the diaphragm, the thickness of the porous membrane is 10-15 microns, the porous membrane has uniform (uniform) pore size distribution, and the pore size is 2~3 microns.
The preparation method comprises the following steps:
the two film materials are combined in a hot pressing mode to form a combined structure with asymmetric structures on two sides.
The battery was assembled using the separator of this example, and the positive and negative electrodes of the battery were prepared as follows:
(1) Preparation of electrodes
Dissolving lithium manganate, a conductive agent and polyvinylidene fluoride (mass ratio 80.
Dissolving graphite, a binder and a thickening agent (mass ratio of 90.
(2) Cutting positive and negative sheets to obtain a positive electrode and a negative electrode with required sizes; the double-layer combined diaphragm of the embodiment is placed between a positive electrode and a negative electrode to be assembled into a battery core in a lamination mode, the battery core is placed into an aluminum plastic film to be manufactured into a soft package battery, and finally an electrolyte solution (mass ratio EC: EMC =1:1 concentration 1M) is injected to be assembled into the battery.
The performance comparison of the battery using the combined diaphragm in the embodiment and the battery using the conventional polypropylene microporous diaphragm (thickness of 20 to 30 micrometers, pore diameter of 0.2 to 0.5 micrometers) is shown in table 1. Both are identical except for the different membranes used.
Evaluation examples: battery performance testing
TABLE 1 comparison of the normal temperature cycle performance of lithium ion batteries by the combined process and the conventional process
Referring to table 1, it is proved that the normal temperature and high temperature cycle performance of the battery using the combined diaphragm prepared by the combined process of the present invention is superior to the performance of the battery using the diaphragm prepared by the conventional process.
Fig. 2 shows the change of the cycle number and the capacity retention rate of the battery at normal temperature.
Example 2
In the combined diaphragm of the embodiment, the microporous membrane is a polypropylene/polyethylene/polypropylene composite membrane, the thickness is 20 to 30 micrometers, and the pore size is about 400 nanometers; the porous membrane is made of polyvinylidene fluoride membrane with high liquid absorption capacity, the liquid absorption capacity is 300% of the self weight of the diaphragm, the thickness of the porous membrane is 10-15 micrometers, and the pore size is 1~5 micrometers.
The method for preparing the battery is the same as that of example 1.
Fig. 3 shows the change of the cycle number and the capacity retention rate of the battery at normal temperature.
The composition, positive and negative electrode composition and battery structure of the lithium ion battery involved in this example are not specific, and the example describes the present invention, but the present invention is not limited to this.
The double-layer combined diaphragm prepared according to the embodiment has micropores and a porous structure, and the uniform porous structure is beneficial to the uniform distribution of electrolyte and the reduction of polarization. According to the utility model discloses the lithium ion battery of preparation has high thermostability, high rich liquid rate, high mechanical strength advantage concurrently.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered by the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A composite separator for a battery, characterized in that: the combined diaphragm is a layer-by-layer combined diaphragm comprising a microporous membrane and a porous membrane, wherein the porous membrane has uniform pore size distribution, and the pore size is 1~5 mu m.
2. The composite diaphragm of claim 1, wherein: the pore size of the porous membrane is 2~3 mu m.
3. The composite diaphragm of claim 1, wherein: the porous membrane is a membrane material with at least one of good thermal stability, high liquid-rich capacity or strong mechanical property, wherein the good thermal stability means that no molten closed pores appear at the temperature of more than 150 ℃, the high-temperature shrinkage rate is less than 5 percent, the high liquid-rich capacity means that the liquid absorption amount is 120 to 400 percent of the self weight of the membrane, and the strong mechanical property means that the tensile strength in the transverse direction and the longitudinal direction is more than 1500Kg/cm 2 。
4. The composite diaphragm of claim 1, wherein: the porous membrane is arranged on one side of the microporous membrane or on both sides of the microporous membrane.
5. The composite diaphragm of claim 1, wherein: the microporous membrane is a single-layer microporous membrane or a multi-layer microporous membrane, and the porous membrane is a single-layer membrane or a multi-layer composite membrane.
6. The composite diaphragm of claim 1, wherein: the pore diameter of the microporous membrane is uniform, and the pore diameter is less than 1 mu m.
7. The composite diaphragm of claim 1, wherein: the microporous membrane is a single-layer PP, single-layer PE or multi-layer PP/PE/PP diaphragm material.
8. The composite diaphragm of claim 1, wherein: the thickness of the microporous membrane is 20 to 40 μm, and the thickness of the microporous membrane is 5 to 15 μm.
9. The composite diaphragm of any one of claims 1 to 8, wherein: the combined diaphragm adopts a microporous membrane/porous membrane double-layer combination, a microporous membrane/porous membrane/microporous membrane three-layer combination or a porous membrane/microporous membrane three-layer combination.
10. A battery comprising a positive electrode, a negative electrode, an electrolyte, and a separator, wherein: the membrane is a combined membrane of any one of claims 1 to 9, and the battery comprises a zinc-manganese battery, a nickel-zinc battery, a nickel-cadmium battery, a silver-zinc battery, a lead-acid battery, a nickel-hydrogen battery, a lithium ion battery and a fuel battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011203306913U CN202333014U (en) | 2011-09-05 | 2011-09-05 | Combined diaphragm for battery and battery applying same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011203306913U CN202333014U (en) | 2011-09-05 | 2011-09-05 | Combined diaphragm for battery and battery applying same |
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| CN202333014U true CN202333014U (en) | 2012-07-11 |
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| CN2011203306913U Expired - Lifetime CN202333014U (en) | 2011-09-05 | 2011-09-05 | Combined diaphragm for battery and battery applying same |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903921A (en) * | 2012-10-31 | 2013-01-30 | 厦门大学 | Aqueous battery using carbon fluoride as anode |
| CN103682208A (en) * | 2012-09-05 | 2014-03-26 | 中国科学院大连化学物理研究所 | Composite membrane for lithium-air battery and preparation thereof |
| CN103779573A (en) * | 2013-12-19 | 2014-05-07 | 深圳市海斯迪电子有限公司 | Double-electrode-layer polymer battery slurry and preparation method thereof |
| CN105874630A (en) * | 2014-01-02 | 2016-08-17 | 达拉米克有限责任公司 | Multilayer separator and methods of manufacture and use |
| CN106129312A (en) * | 2016-09-13 | 2016-11-16 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistance multilayer composite lithium ion cell barrier film |
| CN105226224B (en) * | 2014-07-03 | 2018-01-02 | 中国科学院大连化学物理研究所 | A kind of application of porous ion conductive membranes in lithium-sulfur cell |
| CN109263220A (en) * | 2018-11-02 | 2019-01-25 | 苏州锂盾储能材料技术有限公司 | Nonpolar physics anchoring method polymer soft-package battery aluminum plastic film and its manufacturing method |
| CN110676416A (en) * | 2019-11-08 | 2020-01-10 | 温岭市聚智高分子材料有限公司 | Alkaline battery diaphragm and preparation method thereof |
| US11374286B2 (en) | 2019-03-18 | 2022-06-28 | Ningde Amperex Technology Limited | Separator and electrochemical device |
-
2011
- 2011-09-05 CN CN2011203306913U patent/CN202333014U/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682208A (en) * | 2012-09-05 | 2014-03-26 | 中国科学院大连化学物理研究所 | Composite membrane for lithium-air battery and preparation thereof |
| CN103682208B (en) * | 2012-09-05 | 2016-02-03 | 中国科学院大连化学物理研究所 | A kind of composite membrane for lithium-air battery and preparation thereof |
| CN102903921B (en) * | 2012-10-31 | 2015-09-02 | 厦门大学 | A kind of take fluorocarbons as the water system battery of positive pole |
| CN102903921A (en) * | 2012-10-31 | 2013-01-30 | 厦门大学 | Aqueous battery using carbon fluoride as anode |
| CN103779573A (en) * | 2013-12-19 | 2014-05-07 | 深圳市海斯迪电子有限公司 | Double-electrode-layer polymer battery slurry and preparation method thereof |
| CN112542654A (en) * | 2014-01-02 | 2021-03-23 | 达拉米克有限责任公司 | Multilayer separator and methods of making and using |
| CN105874630A (en) * | 2014-01-02 | 2016-08-17 | 达拉米克有限责任公司 | Multilayer separator and methods of manufacture and use |
| CN105226224B (en) * | 2014-07-03 | 2018-01-02 | 中国科学院大连化学物理研究所 | A kind of application of porous ion conductive membranes in lithium-sulfur cell |
| CN106129312A (en) * | 2016-09-13 | 2016-11-16 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistance multilayer composite lithium ion cell barrier film |
| CN106129312B (en) * | 2016-09-13 | 2019-01-25 | 河北金力新能源科技股份有限公司 | A kind of preparation method of high temperature resistance multilayer composite lithium ion cell diaphragm |
| CN109263220A (en) * | 2018-11-02 | 2019-01-25 | 苏州锂盾储能材料技术有限公司 | Nonpolar physics anchoring method polymer soft-package battery aluminum plastic film and its manufacturing method |
| US11374286B2 (en) | 2019-03-18 | 2022-06-28 | Ningde Amperex Technology Limited | Separator and electrochemical device |
| CN110676416A (en) * | 2019-11-08 | 2020-01-10 | 温岭市聚智高分子材料有限公司 | Alkaline battery diaphragm and preparation method thereof |
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| CX01 | Expiry of patent term |
Granted publication date: 20120711 |