CN107958981B - Composite diaphragm for lithium ion power battery and preparation method - Google Patents
Composite diaphragm for lithium ion power battery and preparation method Download PDFInfo
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- CN107958981B CN107958981B CN201710489398.3A CN201710489398A CN107958981B CN 107958981 B CN107958981 B CN 107958981B CN 201710489398 A CN201710489398 A CN 201710489398A CN 107958981 B CN107958981 B CN 107958981B
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- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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- 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
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- 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
- H01M50/411—Organic material
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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 composite diaphragm for a lithium ion power battery and a preparation method thereof. The micropores are distributed in a gradient level manner, so that the chemical polarization process of the lithium ion battery can be effectively controlled, and good effects on the aspects of larger voltage impact and high temperature resistance of the diaphragm are achieved. The composite diaphragm with different micropore diameters on the two sides enhances the specific surface area of the material, and controls the concentration polarization of lithium ion de-intercalation in the charging and discharging process of the lithium ion power battery, thereby improving the safety performance and prolonging the service life of the lithium ion power battery.
Description
Technical Field
The invention relates to the field of composite diaphragm materials, in particular to a composite diaphragm for a lithium ion power battery and a preparation method thereof.
Background
The lithium ion battery diaphragm is a microporous membrane positioned between the anode and the cathode of the lithium ion battery, and has the main functions of isolating the anode and the cathode to prevent short circuit, and enabling lithium ions to freely pass between the anode and the cathode to ensure the proceeding of electrochemistry. The separator itself does not participate in the battery chemical reaction, but its performance has a significant influence on the safe use of the battery. The existing lithium ion battery diaphragm is generally in a single-layer, double-layer or multi-layer structure and is prepared by adopting a dry method or a wet film-making process. The existing process mainly focuses on how to improve the structure of the separator, such as uniform pore structure, pore distribution, high porosity, etc., so as to improve various performances of the separator. However, most people neglect an important structural problem, namely, no matter the diaphragm is of a single-layer, double-layer or multi-layer structure, when the micropores and the pore structure of the diaphragm are formed, the diaphragm is formed in one step by adopting a one-step extraction or two-way stretching mode, and the pore structure and the size of the micropores formed on the two sides are consistent. Because the rate and the kinetic energy that lithium ion in inside charge-discharge process takes off and inserts are different, the concentration polarizability that forms is also different, consequently, if the micropore aperture size on diaphragm two sides is unanimous, not only can waste the electric energy in the electric polarization process, leads to the cycle life decline of battery, more is unfavorable for power battery's deep discharge simultaneously.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a composite separator for a lithium ion power battery and a preparation method thereof, wherein microporous structures with different pore sizes and uniform distribution are designed on both sides of the separator.
In order to achieve the above purpose, the invention is realized by the following scheme:
a composite diaphragm for a lithium ion power battery is characterized in that a prepolymer I is formed by co-melting an organic pore-forming agent and polyolefin polymer resin, a prepolymer II is formed by co-melting an inorganic pore-forming agent and polyolefin polymer resin, the prepolymer I and the prepolymer II are compounded through a heat conduction roller, and then are compounded and cooled through a cooling roller to form a composite membrane; then, longitudinal and transverse two-way stretching and shaping are adopted, inorganic pore-forming agents in the composite membrane are removed in a water washing and heating mode, organic pore-forming agents in the composite membrane are removed in an extraction mode, and microporous composite structures with different sizes and apertures are respectively formed on the two sides of the membrane; the thickness of the obtained composite diaphragm is 1-5um, the aperture of the micropores on one surface of the composite diaphragm is 5-20nm, the aperture of the micropores on the other surface of the composite diaphragm is 10-100nm, and the micropores are distributed in a gradient level from large to small along the thickness direction.
Further, the organic pore-forming agent is paraffin oil and/or dimethyl silicone oil.
Further, the polyolefin polymer resin is one or more of PI, PE, PP or poly-1-butene.
Further, the inorganic pore-forming agent is one of nano inorganic compounds of ammonium bicarbonate, lithium carbonate or cobalt carbonate, and the particle size of the inorganic compound is 10-100 nm.
The preparation method of the composite diaphragm for the lithium ion power battery is characterized by comprising the following steps:
the method comprises the following steps of (1) dissolving an organic pore-forming agent and polyolefin polymer resin together at the temperature of 180-250 ℃ to form a prepolymer I, wherein the mass ratio of the polyolefin polymer resin to the organic pore-forming agent is 1: (2-4);
and (II) ultrasonically mixing an inorganic pore-forming agent and polyolefin polymer resin through paraffin oil to form a mixture with the viscosity of 10-25Pa & S, and then co-dissolving at the temperature of 180-300 ℃ to form a prepolymer II, wherein the mass ratio of the polyolefin polymer resin to the inorganic pore-forming agent to the paraffin oil is 1: (2-4): (0.8-1);
thirdly, respectively melting the prepolymer I and the prepolymer II, then respectively extruding the melted prepolymers through two independent extruders and uniformly coating the melted prepolymers on the surfaces of a cooling roller 1 and a cooling roller 2, wherein the surface temperatures of the cooling roller 1 and the cooling roller 2 are 30-50 ℃; wherein the thickness of the prepolymer first extrusion film is 50-100um, the thickness of the prepolymer second extrusion film is 100-500um, and the cooling time is 5-10 min;
fourthly, casting the prepolymer I and the prepolymer II which are respectively cooled in the third step to a heat conducting roller surface with the temperature of 80-120 ℃ together, and fusing together, wherein the rotating speed of the heat conducting roller is 5-10m/min, and the diameter of the heat conducting roller is 50-100 cm; cooling the complex body formed by co-melting the prepolymer I and the prepolymer II by a cooling roller 3 to form a composite film; wherein the surface temperature of the cooling roller 3 is 10-25 ℃, the distance between the heat conducting roller and the cooling roller 3 is 2-10cm, the rotating speed of the cooling roller 3 is 2-10m/min, and the diameter of the cooling roller 3 is 80-150 cm;
fifthly, longitudinally and transversely stretching the composite membrane in two directions, heating at the temperature of 150 ℃ and 200 ℃, and heating and drying for 5-10min for shaping;
sixthly, putting the composite membrane after heating and shaping into first-stage cold water for rinsing, wherein the rinsing time is 10-15 min; then, carrying out secondary warm water immersion cleaning, wherein the temperature of the warm water is 50-80 ℃, the immersion cleaning time is 5-10min, and removing the inorganic pore-forming agent;
and (seventhly), soaking the washed composite membrane in the step (six) in a first-stage dichloromethane solution for 10-15min, wherein the proportion of dichloromethane to water is (2-5): 1; and then soaking the mixture in second-stage dichloromethane for 10-15min, wherein the proportion of the dichloromethane to the water is (5-10): and 1, removing the organic pore-forming agent, and finally heating and shaping to obtain the composite diaphragm.
Compared with the prior art, the invention has the advantages that:
1. the preparation method has simple process and is easy to realize large-scale production, and the prepared composite diaphragm has a uniform and ordered double-layer pore diameter arrangement structure.
2. In the preparation process, two pore-forming agents, namely an organic pore-forming agent and an inorganic pore-forming agent, are adopted, and are removed in an extraction and water washing mode, so that microporous composite structures with different sizes and apertures can be respectively formed on the two sides of the diaphragm. The diaphragm of the structure is influenced by concentration polarization in the charging process of the lithium ion battery, the lithium ion embedding speed is controlled, and the stability of the charging current is controlled; the quantity of lithium ions passing through the small holes is small during charging, so that the current during charging is more uniform, and the service life of the battery can be prolonged; in the discharging process of the lithium ion battery, the number of lithium ions passing through large holes is large, the desorption speed of the lithium ions is accelerated, the discharging current is larger, the deep discharging capacity of the battery is improved, and the technical requirement of the power battery is met.
3. The composite diaphragm with different micropore diameters on the two sides enhances the specific surface area of the material, improves the space ion conduction and shock resistance of the material, and has higher application value and prospect in the field of power batteries.
4. In the method, the inorganic pore-forming agent is removed by secondary washing, and the organic pore-forming agent is removed by secondary dichloromethane soaking, so that micropores on the two sides of the diaphragm are distributed in a gradient level from large to small along the thickness direction. The reason is that the inorganic pore-forming agent is removed by secondary washing, and the organic pore-forming agent is removed by secondary dichloromethane soaking, namely, the inorganic particles with large particles are washed away by primary washing, and the washing is rinsing; the second stage of water washing is immersion washing, which washes away small inorganic particles, so that the remaining micropores have a gradient hierarchical distribution. Similarly, the same effect is obtained by the method of soaking with dichloromethane. After the micropores are distributed in a gradient layer, the chemical polarization process of the lithium ion battery can be effectively controlled, and good effects on the aspects of larger voltage impact and high temperature resistance of the diaphragm are achieved.
Drawings
FIG. 1 is a flow chart of the preparation of the composite separator of the present invention
Fig. 2 is a schematic structural view of a composite separator product of the present invention.
Detailed Description
The preparation process of the present invention will be described below with reference to specific embodiments. The following description is only for the purpose of illustrating preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited to the embodiments described in the following description.
The first embodiment is as follows:
the preparation method of the composite diaphragm comprises the following steps:
firstly, mixing the raw materials in a mass ratio of 1: 2, and the dimethyl silicone oil is co-dissolved at the temperature of 180 ℃ to form a prepolymer I.
(II) mixing the components in a mass ratio of 1: 0.8: 2, carrying out ultrasonic mixing on the PE powder, paraffin oil and cobalt carbonate with the particle size of 10nm to form a mixture with the viscosity of 10Pa & S, and then carrying out co-dissolution at the temperature of 180 ℃ to form a prepolymer II.
Thirdly, extruding the prepolymer I after the prepolymer I is dissolved through an extruder, uniformly coating the molten prepolymer I on the surface of a cooling roller 1 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer I is 50 um; and extruding the prepolymer twice through another extruder, uniformly coating the molten prepolymer on the surface of a cooling roller 2 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer twice is 100 mu m.
Fourthly, casting the prepolymer I and the prepolymer II which are respectively cooled in the third step to a heat conducting roller surface with the temperature of 100 ℃ together, and fusing together, wherein the rotating speed of the heat conducting roller is 9m/min, and the diameter of the heat conducting roller is 100 cm; cooling the co-melted complex by a cooling roller 3 with the surface temperature of 15 ℃ to form a composite film; wherein the distance between the heat-conducting roller and the cooling roller 3 is 6cm, the rotating speed of the cooling roller 3 is 8m/min, and the diameter of the cooling roller 3 is 120 cm.
And (V) longitudinally and transversely stretching the composite film in two directions, heating at 160 ℃, and heating and drying for 5.5min for shaping.
Sixthly, putting the composite membrane after heating and shaping into first-stage cold water for rinsing for 12 min; and then the second-stage soaking and washing is carried out for 8min at the temperature of 60 ℃ to remove the cobalt carbonate.
And (seventhly), soaking the washed composite membrane in the step (six) for 15min by using a first-stage dichloromethane solution, wherein the ratio of dichloromethane to water is 4.5: 1; and then soaking for 15min by using second-stage dichloromethane, wherein the ratio of the dichloromethane to the water is 8.5: and 1, removing the dimethyl silicone oil, and finally heating and shaping to obtain the composite diaphragm.
As shown in fig. 2, the thickness of the composite membrane 2 prepared in the first embodiment is 1.5um, the pore diameter of the micropores 3 in the composite membrane 2 is 10nm, the pore diameter of the micropores 1 is 55nm, and the micropores are distributed in a gradient manner from large to small along the thickness direction.
Example two:
the preparation method of the composite diaphragm comprises the following steps:
(II) mixing the components in a mass ratio of 1: 3, and dissolving PP powder and paraffin oil together at 200 ℃ to form a prepolymer I.
(II) mixing the components in a mass ratio of 1: 1: 3, carrying out ultrasonic mixing on PP powder, paraffin oil and lithium carbonate with the particle size of 50nm to form a mixture with the viscosity of 20Pa & S, and then carrying out co-dissolution at the temperature of 240 ℃ to form a prepolymer II.
Thirdly, extruding the prepolymer I after the prepolymer I is dissolved through an extruder, uniformly coating the molten prepolymer I on the surface of a cooling roller 1 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer I is 70 um; and extruding the prepolymer after the second melting through another extruder, uniformly coating the molten prepolymer on the surface of a cooling roller 2 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer second melting is 300 mu m.
Fourthly, casting the prepolymer I and the prepolymer II which are respectively cooled in the third step to a heat conducting roller surface with the temperature of 100 ℃ together, and fusing together, wherein the rotating speed of the heat conducting roller is 7m/min, and the diameter of the heat conducting roller is 100 cm; cooling the co-melted complex by a cooling roller 3 with the surface temperature of 15 ℃ to form a composite film; wherein the distance between the heat-conducting roller and the cooling roller 3 is 6cm, the rotating speed of the cooling roller 3 is 8.5m/min, and the diameter of the cooling roller 3 is 120 cm.
And (V) longitudinally and transversely stretching the composite membrane in a bidirectional way, heating at the temperature of 180 ℃, and heating and drying for 8min for shaping.
Sixthly, putting the composite membrane after heating and shaping into first-stage cold water for rinsing for 13 min; and then carrying out secondary warm water immersion cleaning at the temperature of 75 ℃ for 8min to remove lithium carbonate.
And (seventhly), soaking the washed composite membrane in the step (six) for 15min by using a first-stage dichloromethane solution, wherein the ratio of dichloromethane to water is 4.5: 1; and then soaking for 15min by using second-stage dichloromethane, wherein the ratio of the dichloromethane to the water is 8.5: and 1, removing paraffin oil, and finally heating and shaping to obtain the composite diaphragm.
As shown in fig. 2, the thickness of the composite membrane 2 prepared in example two is 3.8um, the pore diameter of the micropores 3 in the composite membrane 2 is 15nm, the pore diameter of the micropores 1 is 80nm, and the micropores are distributed in a gradient manner from large to small along the thickness direction.
Example three:
the preparation method of the composite diaphragm comprises the following steps:
and (III) mixing the components in a mass ratio of 1: 4, and the paraffin oil are co-dissolved at the temperature of 250 ℃ to form a prepolymer I.
(II) mixing the components in a mass ratio of 1: 1: 4, carrying out ultrasonic mixing on PI powder, paraffin oil and ammonium bicarbonate with the particle size of 90nm to form a mixture with the viscosity of 25Pa & S, and then carrying out co-dissolution at the temperature of 280 ℃ to form a prepolymer II.
Thirdly, extruding the prepolymer after the prepolymer is dissolved through an extruder, uniformly coating the molten prepolymer on the surface of a cooling roller 1 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer is 100 mu m; and extruding the prepolymer twice through another extruder, uniformly coating the molten prepolymer on the surface of a cooling roller 2 with the surface temperature of 35 ℃, and cooling for 8min, wherein the thickness of an extruded film of the prepolymer twice is 500 mu m.
Fourthly, casting the prepolymer I and the prepolymer II which are respectively cooled in the third step to a heat conducting roller surface with the temperature of 100 ℃ together, and fusing together, wherein the rotating speed of the heat conducting roller is 6m/min, and the diameter of the heat conducting roller is 100 cm; cooling the co-melted complex by a cooling roller 3 with the surface temperature of 15 ℃ to form a composite film; wherein the distance between the heat-conducting roller and the cooling roller 3 is 6cm, the rotating speed of the cooling roller 3 is 5m/min, and the diameter of the cooling roller 3 is 120 cm.
And (V) longitudinally and transversely stretching the composite membrane in two directions, heating at the temperature of 200 ℃, and heating, drying and shaping for 9.5 min.
Sixthly, putting the composite membrane after heating and shaping into first-stage cold water for rinsing for 13 min; and then the second-stage soaking and washing is carried out for 8min at the temperature of 75 ℃ to remove ammonium bicarbonate.
And (seventhly), soaking the washed composite membrane in the step (six) for 15min by using a first-stage dichloromethane solution, wherein the ratio of dichloromethane to water is 4.5: 1; and then soaking for 15min by using second-stage dichloromethane, wherein the ratio of the dichloromethane to the water is 8.5: and 1, removing paraffin oil, and finally heating and shaping to obtain the composite diaphragm.
As shown in fig. 2, the thickness of the composite membrane 2 prepared in the third embodiment is 4.8um, the pore diameter of the micropores 3 in the composite membrane 2 is 20nm, the pore diameter of the micropores 1 is 100nm, and the micropores are distributed in a gradient manner from large to small along the thickness direction.
And (3) testing the cycle performance and the charge-discharge capacity of the composite diaphragm prepared in the third embodiment of the invention and the conventional diaphragm, wherein the cycle performance test is to carry out 1C charge-discharge on the lithium ion battery prepared from the composite diaphragm prepared in the third embodiment and the conventional diaphragm at 25 ℃, and the number of times that the capacity attenuation is lower than 90% is detected. The charge and discharge capacity test is to assemble the composite separator prepared in example three and a conventional separator into a lithium ion battery with a capacity of 2000mAh, and to perform a charge and discharge actual capacity test for 60 minutes. The test results were as follows:
Claims (4)
1. a composite diaphragm for a lithium ion power battery is characterized in that a prepolymer I is formed by co-melting an organic pore-forming agent and polyolefin polymer resin, a prepolymer II is formed by co-melting an inorganic pore-forming agent and polyolefin polymer resin, the prepolymer I and the prepolymer II are compounded through a heat conduction roller, and then are compounded and cooled through a cooling roller to form a composite membrane; then, longitudinal and transverse two-way stretching and shaping are adopted, inorganic pore-forming agents in the composite membrane are removed in a water washing and heating mode, organic pore-forming agents in the composite membrane are removed in an extraction mode, and microporous composite structures with different sizes and apertures are respectively formed on the two sides of the membrane; the thickness of the obtained composite diaphragm is 1-5um, the aperture of the micropores on one surface of the composite diaphragm is 5-20nm, the aperture of the micropores on the other surface of the composite diaphragm is 10-100nm, and the micropores are distributed in a gradient level from large to small along the thickness direction; the preparation method of the composite diaphragm comprises the following steps:
the method comprises the following steps of (1) dissolving an organic pore-forming agent and polyolefin polymer resin together at the temperature of 180-250 ℃ to form a prepolymer I, wherein the mass ratio of the polyolefin polymer resin to the organic pore-forming agent is 1: (2-4);
and (II) ultrasonically mixing an inorganic pore-forming agent and polyolefin polymer resin through paraffin oil to form a mixture with the viscosity of 10-25Pa & S, and then co-dissolving at the temperature of 180-300 ℃ to form a prepolymer II, wherein the mass ratio of the polyolefin polymer resin to the inorganic pore-forming agent to the paraffin oil is 1: (2-4): (0.8-1);
thirdly, respectively melting the prepolymer I and the prepolymer II, then respectively extruding the melted prepolymers through two independent extruders and uniformly coating the melted prepolymers on the surfaces of a cooling roller 1 and a cooling roller 2, wherein the surface temperatures of the cooling roller 1 and the cooling roller 2 are 30-50 ℃; wherein the thickness of the prepolymer first extrusion film is 50-100um, the thickness of the prepolymer second extrusion film is 100-500um, and the cooling time is 5-10 min;
fourthly, casting the prepolymer I and the prepolymer II which are respectively cooled in the third step to a heat conducting roller surface with the temperature of 80-120 ℃ together, and fusing together, wherein the rotating speed of the heat conducting roller is 5-10m/min, and the diameter of the heat conducting roller is 50-100 cm; cooling the complex body formed by co-melting the prepolymer I and the prepolymer II by a cooling roller 3 to form a composite film; wherein the surface temperature of the cooling roller 3 is 10-25 ℃, the distance between the heat conducting roller and the cooling roller 3 is 2-10cm, the rotating speed of the cooling roller 3 is 2-10m/min, and the diameter of the cooling roller 3 is 80-150 cm;
fifthly, longitudinally and transversely stretching the composite membrane in two directions, heating at the temperature of 150 ℃ and 200 ℃, and heating and drying for 5-10min for shaping;
sixthly, putting the composite membrane after heating and shaping into first-stage cold water for rinsing, wherein the rinsing time is 10-15 min; then, carrying out secondary warm water immersion cleaning, wherein the temperature of the warm water is 50-80 ℃, the immersion cleaning time is 5-10min, and removing the inorganic pore-forming agent;
and (seventhly), soaking the washed composite membrane in the step (six) in a first-stage dichloromethane solution for 10-15min, wherein the proportion of dichloromethane to water is (2-5): 1; and then soaking the mixture in second-stage dichloromethane for 10-15min, wherein the proportion of the dichloromethane to the water is (5-10): and 1, removing the organic pore-forming agent, and finally heating and shaping to obtain the composite diaphragm.
2. The composite separator for a lithium-ion power battery according to claim 1, wherein the organic pore former is paraffin oil and/or simethicone.
3. The composite separator for a lithium-ion power battery according to claim 1, wherein the polyolefin-based polymer resin is one or more of PI, PE, PP, or poly-1-butene.
4. The composite separator for a lithium-ion power battery as defined in claim 1, wherein the inorganic pore former is one of nano-sized inorganic compounds ammonium bicarbonate, lithium carbonate or cobalt carbonate, and the particle size of the inorganic compound is 10 to 100 nm.
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| CN109830630A (en) * | 2018-12-29 | 2019-05-31 | 深圳中兴新材技术股份有限公司 | Coating diaphragm with hierarchical porous structure and its preparation method and application |
| CN112542653B (en) * | 2019-09-05 | 2023-03-14 | 深圳市拓邦锂电池有限公司 | Anti-wrinkle diaphragm of lithium battery and preparation method thereof |
| CN111001299B (en) * | 2019-12-31 | 2022-03-25 | 江苏厚生新能源科技有限公司 | Aperture asymmetric diaphragm, preparation method and application in seawater desalination |
| CN111653711B (en) * | 2020-05-18 | 2022-05-20 | 苏州大学 | Biomass fiber composite membrane for lithium battery diaphragm and preparation method thereof |
| CN112295420B (en) * | 2020-10-14 | 2022-05-17 | 江苏厚生新能源科技有限公司 | Asymmetric pore structure water filtration membrane and preparation process thereof |
| CN113471623B (en) * | 2021-05-25 | 2023-08-01 | 湖南诺邦新能源科技有限公司 | Trimming treatment method for heat-set lithium battery diaphragm |
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| JPH10279718A (en) * | 1997-04-10 | 1998-10-20 | Nitto Denko Corp | Porous film, separator for battery and battery |
| CN101253232A (en) * | 2005-09-16 | 2008-08-27 | 东燃化学株式会社 | Polyethylene microporous membrane, process for production thereof, and battery separator |
| CN103184013A (en) * | 2011-12-28 | 2013-07-03 | 天津东皋膜技术有限公司 | Polyvinyl composite microporous membrane with thermocompression bonding characteristic |
| CN102751460A (en) * | 2012-05-23 | 2012-10-24 | 杭州福膜新材料科技有限公司 | High-temperature-resisting composite isolation film and preparation method thereof |
| CN103579663A (en) * | 2012-07-24 | 2014-02-12 | 株式会社日立制作所 | Lithium-ion secondary battery |
| CN106328858A (en) * | 2015-06-23 | 2017-01-11 | 辽源鸿图锂电隔膜科技股份有限公司 | Lithium ion battery diaphragm with three kinds of microporous structures, and polyethylene composition adopted by same |
| CN106654351A (en) * | 2015-10-30 | 2017-05-10 | 松下知识产权经营株式会社 | Lithium-ion battery |
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| CN107958981A (en) | 2018-04-24 |
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