CN114024092A - Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof - Google Patents
Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof Download PDFInfo
- Publication number
- CN114024092A CN114024092A CN202111321181.4A CN202111321181A CN114024092A CN 114024092 A CN114024092 A CN 114024092A CN 202111321181 A CN202111321181 A CN 202111321181A CN 114024092 A CN114024092 A CN 114024092A
- Authority
- CN
- China
- Prior art keywords
- stirring
- preparing
- slurry
- diaphragm
- coating
- 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
Images
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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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
- H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses an ice crystallization induced self-assembled porous coating diaphragm and a preparation process thereof, wherein the preparation process comprises the following steps: (1) preparing slurry: mixing paraffin oil, pure water, wetting agent and hydroxyethyl cellulose to prepare slurry; (2) preparing a coating diaphragm: coating the slurry on a base film, performing crisp cooling in liquid nitrogen, freezing at low temperature, extracting, and drying to obtain the coated diaphragm. The coating diaphragm is prepared by the ice crystallization induced self-assembly method, in the process of freezing crystallization, hydroxyethyl cellulose molecules grow at the boundary of ice crystals, and a large amount of the hydroxyethyl cellulose molecules wrap the ice crystals to generate an aggregation phenomenon, so that the self-assembly is induced to form the aggregation phenomenon, and the formation of pores of the coating diaphragm is facilitated.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to an ice crystallization induced self-assembly porous coating diaphragm and a preparation process thereof.
Background
With the development of scientific technology, lithium batteries have become the mainstream. The structure of the lithium battery comprises a positive electrode, a negative electrode, an electrolyte and a battery diaphragm, wherein the positive/negative electrode material is lithium metal or lithium alloy, and a nonaqueous solution is used as the electrolyte. The battery diaphragm is a key inner layer component of the lithium battery, and the performance of the battery diaphragm determines the interface structure, the internal resistance and the like of the manufactured battery, so that the characteristics of the lithium battery, such as capacity, cycle performance, safety performance and the like, are directly influenced. The excellent performance of the battery diaphragm has important significance for improving the comprehensive performance of the battery. The battery diaphragm is mainly used for isolating the positive electrode and the negative electrode of the lithium battery, preventing the two electrodes from contacting and enabling ions in electrolyte to pass through. The commercial lithium battery diaphragm in the market is often a polyolefin diaphragm, such as a PE (polyethylene), PP (polypropylene) microporous membrane, non-woven fabric, aramid fiber and the like, taking a PE diaphragm as an example, the common range of the porosity of the diaphragm is 38-47%, the porosity is low, the affinity to electrolyte is not good, the liquid absorption capacity of the diaphragm is not high, and the liquid absorption capacity of the existing diaphragm with higher liquid absorption capacity reaches 120%; the surface of the diaphragm has strong hydrophobicity, which is not beneficial to the wetting effect; and the surface of the diaphragm is compact, so that the permeation of electrolyte and the passing of ions are not facilitated, and the electrochemical performance of the battery can be reduced. Therefore, we propose an ice crystallization induced self-assembled porous coated separator and a process for preparing the same.
Disclosure of Invention
The present invention aims to provide an ice crystallization induced self-assembled porous coating membrane and a preparation process thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: an ice crystallization induced self-assembled porous coated separator comprising the steps of:
(1) preparing slurry: mixing paraffin oil, pure water and wetting agent, stirring at high speed, adding hydroxyethyl cellulose, heating and stirring to obtain slurry;
(2) preparing a coating diaphragm: coating the slurry on a base film, performing crisp cooling in liquid nitrogen, freezing at low temperature, immersing in ethanol for extraction, and drying to obtain the coated diaphragm.
Further, the method comprises the following steps:
(1) preparing slurry:
mixing paraffin oil, pure water and wetting agent, and stirring at high speed, wherein the process comprises the following steps: stirring at the rotating speed of 1000-3000 rpm for 3-6 h;
adding hydroxyethyl cellulose, heating and stirring, and the process comprises the following steps: stirring at the temperature of 45-65 ℃ and the stirring speed of 1000-3000 rpm for 5-8 h to prepare slurry;
(2) preparing a coating diaphragm: coating the slurry on a base film, carrying out brittle cooling in liquid nitrogen for 30-60 min, putting the base film into a refrigerator for freezing for 6-12 h, wherein the freezing temperature is-38 to-7 ℃, immersing the base film into ethanol for extraction, and drying the base film at the temperature of 60-80 ℃ to obtain the coated diaphragm.
Further, the method comprises the following steps:
(1) preparing slurry:
mixing paraffin oil, pure water, wetting agent and surfactant, and stirring at high speed, wherein the process comprises the following steps: stirring at the rotating speed of 1000-3000 rpm for 3-6 h;
adding hydroxyethyl cellulose, heating and stirring, and the process comprises the following steps: stirring at the temperature of 45-65 ℃ and the stirring speed of 1000-3000 rpm for 5-8 h to prepare slurry; the wetting agent is added to reduce the surface tension of the slurry, so that the slurry can be coated on the surface of the diaphragm more easily;
(2) preparing a coating diaphragm: coating the slurry on a base film to obtain a diaphragm, carrying out brittle cooling in liquid nitrogen for 30-60 min, and shaping the diaphragm by using the extreme-speed cooling of the liquid nitrogen; putting the mixture into a refrigerator for freezing for 6-12 h, wherein the freezing temperature is-38 to-7 ℃, the step is a key process for forming pores, in the process of freezing and crystallizing, hydroxyethyl cellulose (HEC) separated from phases not only grows at the boundary of ice crystals, but also wraps the ice crystals in a large amount, self-assembly is induced to occur, an aggregation phenomenon is formed, and meanwhile, liquid paraffin droplets are firmly blocked in the own body phase by abundant hydroxyethyl cellulose; immersing the membrane in ethanol for extraction, washing out paraffin oil in the membrane, enabling a pore structure formed by liquid paraffin droplets to be more and more obvious, drying at the temperature of 60-80 ℃ to obtain a coated membrane, and greatly improving the liquid absorption amount and the conductivity of the coated membrane prepared by using an ice crystallization induced self-assembly method, reducing the contact angle, enhancing the hydrophilicity, forming a porous structure on the surface and increasing the porosity of the coated membrane.
Further, the mass ratio of the paraffin oil, the pure water, the surfactant and the hydroxyethyl cellulose is 0.15: 100: (0.03-0.08): (1-5).
Hydroxyethyl cellulose is one of cellulose derivatives, is prepared by etherification of alkaline cellulose and ethylene oxide, is a water-soluble natural nontoxic polymer, has the characteristics of good thickening, suspension, dispersion, emulsification, adhesion, film formation, moisture protection and the like, and can be used for preparing solutions with different viscosity ranges;
with the increase of the HEC content, the morphology of the coated separator surface is different, ranging from disordered fibrous to ordered porous to dense porous. This is because at low HEC concentrations, ice crystals account for the majority of the entire system, there is less but sparse hydroxyethyl cellulose growing at the ice crystal boundaries, liquid paraffin droplet templates dispersed in the emulsion cannot be locked by hydroxyethyl cellulose, run off with freeze-drying and extraction processes, and finally only disordered but sparse hydroxyethyl cellulose remains, when the concentration of the hydroxyethyl cellulose is increased, the host and the guest of the system are inverted, and then the hydroxyethyl cellulose accounts for the host, in the process of freezing crystallization, hydroxyethyl cellulose separated from the phase grows not only at the boundary of ice crystals, meanwhile, a great amount of ice crystals are wrapped to generate aggregation, and simultaneously, the abundant hydroxyethyl cellulose firmly seals liquid paraffin drops in the own body phase, thus, after freeze drying and extraction, the pore structure formed by the liquid paraffin droplets becomes more and more obvious;
the hydroxyethyl cellulose contains abundant-OH and C-O-C functional groups, the functional groups have good affinity with electrolyte, and the porous fibrous HEC increases the porosity of the coated diaphragm, is beneficial to physically adsorbing the electrolyte and obviously improves the liquid absorption of the prepared coated diaphragm; the hydroxyethyl cellulose chain is provided with a large number of hydroxyl groups and other groups with strong polarity, so that the hydrophilicity of the prepared coating diaphragm can be improved;
further, the wetting agent is polysorbate 80, and the base film is polyolefin.
Further, the surfactant is one or more of organic silicon ether surfactants, anionic surfactants and nonionic surfactants.
Further, the anionic surfactant is one of alkyl aryl sodium sulfonate, butyl naphthalene sodium sulfonate, hydroxyethyl sodium sulfonate and sodium dodecyl sulfonate.
Further, the nonionic surfactant is one of long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, polyoxyethylene alkylolamide and fatty alcohol-polyoxyethylene ether.
Further, the coating mode in the step (2) is one of gravure roll coating, narrow slit extrusion coating and dip coating.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the preparation process of the ice crystallization induced self-assembly porous coating diaphragm, the slurry containing the hydroxyethyl cellulose is prepared and coated on the surface of the polyolefin base membrane to prepare the diaphragm, the hydroxyethyl cellulose contains abundant-OH and C-O-C functional groups, so that the hydroxyethyl cellulose has good affinity with electrolyte, and the porous fibrous hydroxyethyl cellulose increases the porosity of the diaphragm, is beneficial to physically adsorbing the electrolyte and greatly improves the liquid absorption of the prepared coating diaphragm.
2. According to the preparation process of the ice crystallization induced self-assembly porous coating diaphragm, the coating diaphragm is prepared by an ice crystallization induced self-assembly method, in the process of freezing crystallization, hydroxyethyl cellulose molecules grow at the boundary of ice crystals, and meanwhile, a large number of ice crystals are wrapped by the hydroxyethyl cellulose molecules to generate an aggregation phenomenon, so that the self-assembly is induced to form the aggregation phenomenon, and the formation of pores of the coating diaphragm is facilitated.
3. According to the preparation process of the ice crystallization induced self-assembly porous coating diaphragm, the prepared slurry contains paraffin oil, during the cooling crystallization process, the liquid paraffin droplets are sealed and locked in the body phase of the slurry by abundant hydroxyethyl cellulose, and through freeze drying and extraction, the pore structure formed by the liquid paraffin droplets is more and more obvious, so that the porosity of the coating diaphragm is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an electron micrograph of example 1 of the present invention;
FIG. 2 is an electron micrograph of example 2 of the present invention;
FIG. 3 is an electron micrograph of example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following polyolefin base films are PE polyolefin microporous films.
Example 1
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours;
adding 1 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, freezing in a refrigerator for 8h at-18 ℃, soaking in ethanol for extraction, and drying at 70 ℃ to obtain the coated diaphragm.
Example 2
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours;
adding 3 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, freezing in a refrigerator for 8h at-18 ℃, soaking in ethanol for extraction, and drying at 70 ℃ to obtain the coated diaphragm.
Example 3
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, freezing in a refrigerator for 8h at-18 ℃, soaking in ethanol for extraction, and drying at 70 ℃ to obtain the coated diaphragm.
Example 4
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: stirring at 1000rpm for 3 h;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 45 ℃ and the rotating speed of 1000rpm for 5 hours to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, freezing in a refrigerator at-7 deg.C for 6h, extracting with ethanol, and oven drying at 60 deg.C to obtain the coated membrane.
Example 5
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: stirring at 3000rpm for 6 h;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at 65 ℃ and 3000rpm for 8h to obtain slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 60min, freezing in a refrigerator at-38 deg.C for 12h, extracting with ethanol, and oven drying at 80 deg.C to obtain the coated membrane.
Example 6
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water, 0.06 kg of wetting agent and 0.06 kg of surfactant, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours; wherein the surfactant is a mixture of organic silicon ether surfactant, anionic surfactant and nonionic surfactant, the anionic surfactant is sodium alkyl aryl sulfonate, and the nonionic surfactant is long-chain fatty alcohol-polyoxyethylene ether;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, freezing in a refrigerator for 8h at-18 ℃, soaking in ethanol for extraction, and drying at 70 ℃ to obtain the coated diaphragm.
Comparative example 1
Taking a PE polyolefin microporous membrane as a diaphragm.
Comparative example 2
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, freezing in a refrigerator at-18 deg.C for 8h, extracting with ethanol, and oven drying at 70 deg.C to obtain the coated membrane.
Comparative example 3
(1) Preparing slurry:
taking 0.15 kg of paraffin oil, 100 kg of pure water and 0.06 kg of wetting agent, and stirring at a high speed, wherein the process comprises the following steps: the stirring speed is 2000rpm, and the stirring time is 3 hours;
adding 5 kg of hydroxyethyl cellulose, heating and stirring, wherein the process comprises the following steps: stirring at the temperature of 55 ℃ and the rotating speed of 2000rpm for 5h to prepare slurry; the wetting agent is polysorbate 80;
(2) preparing a coating diaphragm: coating the slurry on a polyolefin base film, performing brittle cooling in liquid nitrogen for 30min, soaking in ethanol for extraction, and drying at 70 ℃ to obtain the coated diaphragm.
Experiment of
The coated separators/separators obtained in examples 1 to 6 and comparative examples 1 to 3 were taken to prepare samples, and the properties thereof were measured and the measurement results were recorded, respectively:
from the data in the table above, it is clear that the following conclusions can be drawn:
the coated separators obtained in examples 1 to 6 were compared with those obtained in comparative examples 1 to 3, and the results of the examination revealed that:
1. compared with the coated diaphragm obtained in the comparative example 1, the coated diaphragms obtained in the examples 1 to 6 have greatly improved liquid absorption capacity and ion conductivity data, and obviously reduced contact angles, which fully shows that the invention realizes the improvement of liquid absorption and hydrophilicity of the prepared coated diaphragms, and improves the permeation and ion passing performance of electrolyte;
the coated membranes obtained in examples 1-3 have different morphologies from disordered fibrous to ordered porous and to dense porous as the HEC content increases, because at low HEC concentration, the ice crystals occupy most of the whole system, and the HEC molecules growing at the ice crystal boundaries are sparse and few, so that the liquid paraffin droplet templates dispersed in the emulsion cannot be locked by HEC molecules, and run off with the freeze-drying and extraction processes, and only disordered and sparse HEC molecules remain, while when the HEC concentration increases, the host and guest of the system are inverted, and at this time, the HEC molecules occupy the host, and during the freeze crystallization, the HEC molecules separated from the phases not only grow at the ice crystal boundaries, but also wrap a large amount of ice crystals, and aggregation occurs, and meanwhile, abundant HEC molecules firmly lock the liquid paraffin droplets in their own phase, thus, after freeze drying and extraction, the pore structure formed by the liquid paraffin droplets becomes more and more obvious;
the coated separators obtained in examples 3 to 6 were different in the parameter settings in the manufacturing process, and example 6 added the component surfactant, which changed the liquid absorption amount, ionic conductivity, and contact angle data, but still had good electrolyte permeation and ion passage properties;
2. compared with example 3, the morphology of the coated diaphragm obtained in comparative examples 2-3 is not much different from that of example 3, but the data of liquid absorption, ionic conductivity and contact angle are obviously changed, which indicates that the coated diaphragm obtained in comparative examples 2-3 has more ineffective pores, and the permeation of electrolyte and the passing of ions are hindered, which fully indicates that the process setting of brittle cooling and freezing in the preparation process of the invention has obvious assistance to the improvement of the performance of the prepared coated diaphragm.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation process of an ice crystallization induced self-assembled porous coating diaphragm is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing slurry: mixing paraffin oil, pure water and wetting agent, stirring at high speed, adding hydroxyethyl cellulose, heating and stirring to obtain slurry;
(2) preparing a coating diaphragm: coating the slurry on a base film, performing crisp cooling in liquid nitrogen, freezing at low temperature, immersing in ethanol for extraction, and drying to obtain the coated diaphragm.
2. The process of claim 1 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the method comprises the following steps:
(1) preparing slurry:
mixing paraffin oil, pure water and wetting agent, and stirring at high speed, wherein the process comprises the following steps: stirring at the rotating speed of 1000-3000 rpm for 3-6 h;
adding hydroxyethyl cellulose, heating and stirring, and the process comprises the following steps: stirring at the temperature of 45-65 ℃ and the stirring speed of 1000-3000 rpm for 5-8 h to prepare slurry;
(2) preparing a coating diaphragm: coating the slurry on a base film, carrying out brittle cooling in liquid nitrogen for 30-60 min, putting the base film into a refrigerator for freezing for 6-12 h, wherein the freezing temperature is-38 to-7 ℃, immersing the base film into ethanol for extraction, and drying the base film at the temperature of 60-80 ℃ to obtain the coated diaphragm.
3. The process of claim 2 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the method comprises the following steps:
(1) preparing slurry:
mixing paraffin oil, pure water, wetting agent and surfactant, and stirring at high speed, wherein the process comprises the following steps: stirring at the rotating speed of 1000-3000 rpm for 3-6 h;
adding hydroxyethyl cellulose, heating and stirring, and the process comprises the following steps: stirring at the temperature of 45-65 ℃ and the stirring speed of 1000-3000 rpm for 5-8 h to prepare slurry;
(2) preparing a coating diaphragm: coating the slurry on a base film, carrying out brittle cooling in liquid nitrogen for 30-60 min, putting the base film into a refrigerator for freezing for 6-12 h, wherein the freezing temperature is-38 to-7 ℃, immersing the base film into ethanol for extraction, and drying the base film at the temperature of 60-80 ℃ to obtain the coated diaphragm.
4. The process of claim 3 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the mass ratio of the paraffin oil, the pure water, the surfactant and the hydroxyethyl cellulose is 0.15: 100: (0.03-0.08): (1-5).
5. The process of claim 1 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the wetting agent is polysorbate 80.
6. The process of claim 3 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the surfactant is one or more of organic silicon ether surfactant, anionic surfactant and nonionic surfactant.
7. The process of claim 6 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the anionic surfactant is one of alkyl aryl sodium sulfonate, butyl naphthalene sodium sulfonate, hydroxyethyl sodium sulfonate and dodecyl sodium sulfonate.
8. The process of claim 6 for preparing an ice crystallization induced self-assembled porous coated separator, wherein: the nonionic surfactant is one of long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, polyoxyethylene alkylolamide and fatty alcohol-polyoxyethylene ether.
9. A coated separator made by the process of any one of claims 1-8 for making an ice crystallization induced self-assembled porous coated separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111321181.4A CN114024092A (en) | 2021-11-09 | 2021-11-09 | Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111321181.4A CN114024092A (en) | 2021-11-09 | 2021-11-09 | Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114024092A true CN114024092A (en) | 2022-02-08 |
Family
ID=80062839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111321181.4A Pending CN114024092A (en) | 2021-11-09 | 2021-11-09 | Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114024092A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001283813A (en) * | 2000-03-29 | 2001-10-12 | Mitsubishi Paper Mills Ltd | Separator for battery and battery |
| US20050164025A1 (en) * | 2003-09-26 | 2005-07-28 | Pti Advanced Filtration, Inc. | Semipermeable hydrophilic membrane |
| CN102188749A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | 3D porous bracket with mesoporous biological glass coating and preparation method thereof |
| CN104861199A (en) * | 2015-06-16 | 2015-08-26 | 广东工业大学 | Method for preparing environment-friendly hydrophilic porous coating used for modifying surface of porous membrane |
| CN105393383A (en) * | 2013-10-31 | 2016-03-09 | Lg化学株式会社 | Method for preparing separation membrane for electrochemical device, and separation membrane for electrochemical device prepared thereby |
| CN108172745A (en) * | 2018-01-05 | 2018-06-15 | 杨晓丽 | A kind of preparation method of lithium ion battery separator |
| CN112851991A (en) * | 2021-01-08 | 2021-05-28 | 江苏厚生新能源科技有限公司 | Diaphragm and preparation method and application thereof |
| CN112952291A (en) * | 2021-01-29 | 2021-06-11 | 江苏厚生新能源科技有限公司 | Lithium ion diaphragm containing lithium carbonate coating and preparation method thereof |
| CN113097649A (en) * | 2021-03-29 | 2021-07-09 | 江苏厚生新能源科技有限公司 | High-liquid-absorption diatomite-PVA (polyvinyl alcohol) coated membrane and preparation method thereof |
-
2021
- 2021-11-09 CN CN202111321181.4A patent/CN114024092A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001283813A (en) * | 2000-03-29 | 2001-10-12 | Mitsubishi Paper Mills Ltd | Separator for battery and battery |
| US20050164025A1 (en) * | 2003-09-26 | 2005-07-28 | Pti Advanced Filtration, Inc. | Semipermeable hydrophilic membrane |
| CN102188749A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | 3D porous bracket with mesoporous biological glass coating and preparation method thereof |
| CN105393383A (en) * | 2013-10-31 | 2016-03-09 | Lg化学株式会社 | Method for preparing separation membrane for electrochemical device, and separation membrane for electrochemical device prepared thereby |
| CN104861199A (en) * | 2015-06-16 | 2015-08-26 | 广东工业大学 | Method for preparing environment-friendly hydrophilic porous coating used for modifying surface of porous membrane |
| CN108172745A (en) * | 2018-01-05 | 2018-06-15 | 杨晓丽 | A kind of preparation method of lithium ion battery separator |
| CN112851991A (en) * | 2021-01-08 | 2021-05-28 | 江苏厚生新能源科技有限公司 | Diaphragm and preparation method and application thereof |
| CN112952291A (en) * | 2021-01-29 | 2021-06-11 | 江苏厚生新能源科技有限公司 | Lithium ion diaphragm containing lithium carbonate coating and preparation method thereof |
| CN113097649A (en) * | 2021-03-29 | 2021-07-09 | 江苏厚生新能源科技有限公司 | High-liquid-absorption diatomite-PVA (polyvinyl alcohol) coated membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 廖海洋: "锂离子电池隔膜的制备与改性研究", 《中国优秀博硕学位论文全文数据库（博士） 工程科学I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109585947B (en) | Lithium metal negative electrode double-protection method and application | |
| CN112151762B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and preparation method thereof, and lithium-sulfur battery | |
| CN109841899B (en) | Preparation method of three-dimensional network polymer gel electrolyte membrane based on bacterial cellulose | |
| CN108063279A (en) | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte | |
| Yan et al. | Fabrication of a nano-Li+-channel interlayer for high performance Li–S battery application | |
| CN111029515B (en) | Sulfonated graphene oxide-based single-ion polymer electrolyte membrane and preparation method and application thereof | |
| CN111584810A (en) | Application of mixed cellulose ester film, prepared battery and preparation method | |
| CN111644081A (en) | Preparation method of novel high-stability composite nanofiltration membrane | |
| CN114188668B (en) | Coating slurry, preparation method thereof, composite diaphragm and lithium ion battery | |
| CN114649560A (en) | Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof | |
| CN114024092A (en) | Ice crystallization induced self-assembly porous coating diaphragm and preparation process thereof | |
| CN107369802B (en) | Cellulose coating lithium ion battery diaphragm and preparation method thereof | |
| CN110752337A (en) | Composite diaphragm, preparation method and application thereof | |
| CN117175138A (en) | Preparation method of functionalized nano cellulose membrane | |
| CN112952295B (en) | Polyolefin-cellulose composite diaphragm and preparation method thereof | |
| CN114696035B (en) | Cellulose-based composite diaphragm for lithium ion battery and preparation method thereof | |
| Shi et al. | Advanced porous polyphenylsulfone membrane with ultrahigh chemical stability and selectivity for vanadium flow batteries | |
| CN111192991A (en) | MFI-PAN (melt flow index-Polyacrylonitrile) diaphragm and preparation method and application thereof | |
| CN113328202B (en) | Honeycomb high-porosity and large-aperture lithium battery diaphragm and preparation method thereof | |
| CN111293255A (en) | Modified diaphragm for lithium-sulfur battery and preparation method thereof | |
| CN114243209A (en) | Composite diaphragm material and preparation method and application thereof | |
| CN114335885A (en) | NiPc/PVDF modified PE diaphragm and preparation method thereof | |
| CN111463389A (en) | SiO (silicon dioxide)2@ PAN diaphragm and preparation method and application thereof | |
| CN114447524B (en) | Sesbania gum lithium ion battery diaphragm and preparation method and application thereof | |
| CN114914630B (en) | Polymer composite diaphragm based on nitrogen-containing heterocyclic ionic liquid and application of polymer composite diaphragm in lithium-sulfur battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220208 |
|
| RJ01 | Rejection of invention patent application after publication |