CN109384949B - Preparation process of composite polymer diaphragm for lithium battery - Google Patents
Preparation process of composite polymer diaphragm for lithium battery Download PDFInfo
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a preparation process of a composite polymer diaphragm for a lithium battery, which comprises the following preparation processes: adding the prepared high-strength super-hydrophilic polyurethane into an extruder, melting at 150 ℃, extruding, stretching to form a parallel flaky crystal structure, separating the sheets by heat treatment and stretching again to form micropores, and finally performing heat setting to obtain a high-strength microporous polyurethane membrane; dissolving the prepared surface amination nano ceramic powder in water, then soaking the prepared high-strength microporous polyurethane film in water, ultrasonically oscillating for 30min, then dropwise adding hexamethylene diisocyanate, reacting for 2h, taking out, washing with ethanol, and drying to obtain the composite polymer diaphragm. The nano ceramic powder on the surface of the composite membrane prepared by the method is uniformly dispersed, so that the composite membrane has uniform gaps and uniform mechanical properties and high temperature resistance, and meanwhile, the prepared composite membrane has high wettability and can ensure the passing of electrolyte.
Description
Technical Field
The invention belongs to the field of preparation of lithium battery diaphragms, and relates to a preparation process of a composite polymer diaphragm for a lithium battery.
Background
The diaphragm can let lithium ion pass through positive negative pole of separation simultaneously as one of the important subassembly of lithium cell, prevents the short circuit, and the absorption of the electrolyte is influenced to the height of the imbibition performance of diaphragm simultaneously, because the diaphragm is as ion channel, must ensure the passing through of electrolyte, and whether mechanical properties and the high temperature resistance performance of diaphragm have decided the diaphragm and can cause the damage under adverse circumstances simultaneously, and the diaphragm damage causes the short circuit of lithium cell easily.
In the prior art, a layer of inorganic high-temperature-resistant coating is usually coated on the surface of a composite membrane by dipping or coating in the process of preparing the membrane, so that the pore size of a gap of the composite membrane can be reduced, and the mechanical strength and the high-temperature resistance of the membrane can be improved, but because the inorganic material is adhered to the surface of the polymer membrane by an adhesive, the coating uniformity of the coating and the dispersion uniformity of the inorganic material influence the performance of the prepared membrane in the coating and dispersion processes, when the membrane is not uniformly dispersed or coated uniformly, the performance of different positions of the membrane is easily reduced, and further the membrane is easily subjected to high-temperature melting damage or external force tearing damage in different positions under a severe environment, and meanwhile, in order to realize the high liquid absorption capacity of the membrane, the wetting hydrophilic performance of the membrane must be ensured, for high-strength, the composite membrane has low wettability and low mechanical strength for cellulosic substrates with good wettability properties.
Disclosure of Invention
The invention aims to provide a preparation process of a composite polymer diaphragm for a lithium battery, the polymer diaphragm takes prepared high-strength super-hydrophilic polyurethane as a matrix, as nano ceramic powder is fixed on the surface of a polyurethane film through chemical crosslinking, the binding capacity is strong, the nano ceramic powder can not be separated under the action of external force and high temperature, simultaneously, compared with the ceramic powder directly fixed through bonding, the ceramic powder fixed through chemical crosslinking is uniformly distributed, as the ceramic powder has higher strength and high temperature resistance, the high temperature resistance and strength of the prepared composite film can be improved by fixing a layer of ceramic powder on the two surfaces of the composite film, and as the sleeve system powder is uniformly distributed, the high temperature resistance and strength of the composite film are uniformly distributed, the ceramic powder is prevented from being non-uniformly distributed when the composite film is directly bonded and fixed through a bonding agent in the traditional technology, cause high temperature resistant and the intensity inhomogeneous of the different positions of complex film of preparation to the position of blockking of the micropore on complex film surface is different, make the aperture distribution on complex film surface inhomogeneous, and then have certain influence to the performance of battery, it causes coating or dispersion inhomogeneous directly to coat inorganic material on the diaphragm through the coating method among the prior art to have solved, and then make the different position performance of diaphragm of preparation reduce, and then cause the diaphragm under adverse circumstances, the problem that high temperature melting damage or external force tear damage appear easily in different positions.
The diaphragm prepared by the invention contains a large amount of amino groups, and the surface of the surface amination nano ceramic powder also contains a large amount of amino groups, under the crosslinking action of hexamethylene diisocyanate, the surface amination nano ceramic powder is crosslinked and fixed on the high-strength microporous polyurethane film, so that the nano ceramic powder shields micropores on the microporous polyurethane film, the aperture of the polyurethane film is further reduced, the short circuit caused by contact of the anode and the cathode of the battery due to overlarge aperture is prevented, the aperture is uniformly dispersed, and the problem that the short circuit is caused by large local aperture due to nonuniform aperture of the diaphragm in the diaphragm prepared by a coating or dipping method in the prior art is solved.
Each polymer monomer prepared by the method contains two sulfonic acid groups, and each polymer monomer contains-C-conjugated group, so that the polymerized polyurethane contains a large number of sulfonic acid groups and-C-conjugated group, and the polyurethane has super-hydrophilicity due to the fact that the sulfonic acid groups have high hydrophilic capacity, and the polyurethane has high mechanical strength, thermal stability and high hydrophilicity under the action of the-C-conjugated group, so that the problems that hydrophilic wettability and high mechanical performance cannot be simultaneously realized by an existing composite membrane preparation matrix are solved.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of a composite polymer diaphragm for a lithium battery comprises the following preparation processes:
step one, preparing high-strength super-hydrophilic polyurethane: weighing a certain amount of 1, 5-naphthalenedisulfonic acid disodium salt, dissolving in water, heating to 80 ℃, adding thionyl chloride, performing reflux reaction for 5 hours, separating liquid, retaining a water phase, and performing evaporative crystallization on the water phase to obtain 1, 5-naphthalenedisulfonyl chloride, wherein the reaction structural formula is as follows: wherein, each gram of 1, 5-naphthalene disulfonic acid sodium is added with 7-8mL of water, and added with 2.9-3g of thionyl chloride;
weighing a certain amount of glutamic acid, dissolving the glutamic acid in 1% dilute hydrochloric acid by mass fraction to prepare a glutamic acid solution, adding the prepared glutamic acid solution into a reaction container, heating to 70 ℃, simultaneously adding the 1, 5-naphthalene disulfonyl chloride prepared in the step I into the reaction container, reacting for 3 hours at constant temperature, then evaporating and crystallizing, simultaneously washing crystals by using an acetone solution, and then drying to obtain a cross-linked dicarboxy polymerization monomer, wherein the reaction structural formula is as follows, 15mL of 1% dilute hydrochloric acid by mass fraction is added into every gram of glutamic acid, and 0.73-0.75g of 1, 5-naphthalene disulfonyl chloride is added; the glutamic acid contains primary amine groups, and can perform substitution reaction with sulfonyl chloride at a certain temperature, and the 1, 5-naphthalene disulfonyl chloride contains two sulfonyl chloride functional groups and can be used for crosslinking two glutamic acid molecules at the same time, so that carboxyl groups at two ends of the two glutamic acid molecules in the formed monomer can perform polymerization reaction, and simultaneously two sulfonate ions are introduced into each monomer after the 1, 5-naphthalene disulfonyl chloride is crosslinked, so that the monomer has high hydrophilic performance, and meanwhile, the two monomer molecules are crosslinked through the 1, 5-naphthalene disulfonyl chloride, so that the naphthalene functional groups are introduced into each monomer molecule and contain-C-conjugated groups, so that the strength of the polymerized monomer can be improved, and the thermal stability of the polymerized monomer can be improved;
dissolving the cross-linked dicarboxyl polymerization monomer prepared in the step II in water, adding the cross-linked dicarboxyl polymerization monomer into a reaction container, adding a certain amount of molecular weight regulator into the reaction container, uniformly mixing, heating to 120 ℃, dropwise adding an ethylenediamine solution into the reaction container while controlling the temperature to rise, controlling the dropping speed to be 10-11 mL/min, controlling the temperature to rise by 30 ℃ per hour, stopping heating until the temperature rises to 260 ℃, then reacting at a constant temperature for 1-1.5h, cooling to 70 ℃, discharging the material to obtain the high-strength super-hydrophilic polyurethane, wherein the reaction structural formula is as follows, 0.06g of molecular weight regulator is added into each gram of cross-linked dicarboxyl polymerization monomer, 2.5-2.6mL of ethylenediamine is added, and the molecular weight regulator is dodecyl mercaptan; because each polymerized monomer contains two sulfonic acid groups and-C-conjugated group, the polymerized polyurethane contains a large number of sulfonic acid groups and-C-conjugated group groups, the polyurethane has super-hydrophilicity because the sulfonic acid groups have high hydrophilic capacity, and the polyurethane has high mechanical strength and thermal stability because of the action of the-C-conjugated group;
secondly, adding the high-strength super-hydrophilic polyurethane prepared in the first step into an extruder, melting the polyurethane at 150 ℃, extruding the polyurethane, stretching the polyurethane to form a parallel flaky crystal structure, separating the sheets by heat treatment and stretching the crystal layer again to form elongated micropores, and finally performing heat setting to obtain the high-strength microporous polyurethane membrane;
step three, preparing surface amination nano ceramic powder: weighing a certain amount of nano ceramic powder, adding the nano ceramic powder into water, ultrasonically dispersing the nano ceramic powder uniformly, adding a certain amount of ethylenediamine into the nano ceramic powder, stirring and mixing the mixture uniformly, dropwise adding bisphenol A epoxy resin liquid while stirring violently, reacting the mixture at constant temperature for 1 hour after the nano ceramic powder is completely dropwise added, and then filtering and washing the mixture to obtain surface aminated nano ceramic powder; wherein, 13mL of water is added into each gram of nano ceramic powder, 0.53-0.55g of ethylenediamine is added, and 1.21-1.25g of bisphenol A epoxy resin liquid is added;
fourthly, dissolving the surface aminated nano ceramic powder prepared in the third step in water, performing ultrasonic dispersion uniformly, soaking the high-strength microporous polyurethane membrane prepared in the second step in water, performing ultrasonic oscillation for 30min, then dropwise adding hexamethylene diisocyanate while performing ultrasonic reaction, performing ultrasonic reaction for 2h after complete dropwise addition, taking out the high-strength microporous polyurethane membrane, washing with ethanol, and drying to obtain a composite polymer diaphragm, wherein the reaction structural formula is as follows, each gram of surface aminated nano ceramic powder is added into 7mL of water, each gram of surface aminated nano ceramic powder is added into 2.15-2.18g of surface aminated nano ceramic powder, and each gram of high-strength microporous polyurethane membrane is added with 1.36-1.38g of hexamethylene diisocyanate; because the high-strength microporous polyurethane film contains a large amount of amino groups, and the surface of the surface aminated nano ceramic powder also contains a large amount of amino groups, the surface aminated nano ceramic powder is fixed on the high-strength microporous polyurethane film in a crosslinking manner under the crosslinking action of hexamethylene diisocyanate, so that the nano ceramic powder shields micropores on the microporous polyurethane film, the pore diameter of the polyurethane film is further reduced, and the short circuit caused by the contact of a positive electrode and a negative electrode of a battery due to the overlarge pore diameter is prevented; meanwhile, as the nano ceramic powder is fixed on the surface of the polyurethane film through chemical crosslinking, the nano ceramic powder has strong binding capacity and can not be separated under the action of external force and high temperature, and simultaneously compared with the ceramic powder which is directly fixed through bonding, the ceramic powder which is fixed through chemical crosslinking is uniformly distributed, as the ceramic powder has higher strength and high temperature resistance, the high temperature resistance and strength of the prepared composite film can be improved by fixing a layer of ceramic powder on two surfaces of the composite film, and as the sleeve system powder is uniformly distributed, the high temperature resistance and strength of the composite film are uniformly distributed, the problem that the ceramic powder is not uniformly distributed when the composite film is directly bonded and fixed through an adhesive in the traditional technology is prevented, the high temperature resistance and the strength of different positions of the prepared composite film are not uniform, and the blocking positions of micropores on the surface of the composite film are different, so, and further has some influence on the performance of the battery.
The invention has the beneficial effects that:
the polymer diaphragm prepared by the invention takes the prepared high-strength super-hydrophilic polyurethane as a matrix, because the nano ceramic powder is fixed on the surface of the polyurethane film through chemical crosslinking, the polymer diaphragm has strong bonding capability and can not be separated under the action of external force and high temperature, and simultaneously compared with the ceramic powder directly fixed through bonding, the ceramic powder fixed through chemical crosslinking is uniformly distributed, because the ceramic powder has higher strength and high temperature resistance, the high temperature resistance and strength of the prepared composite film can be improved by fixing a layer of ceramic powder on two surfaces of the composite film, and because the sleeve system powder is uniformly distributed, the high temperature resistance and strength of the composite film are uniformly distributed, the high temperature resistance and strength of the prepared composite film are prevented from being non-uniformly distributed when the composite film is directly bonded and fixed through an adhesive in the prior art, so that the high temperature resistance and the strength of different positions of the prepared composite, and the positions of the micropores on the surface of the composite film are different in blocking, so that the pore diameter distribution on the surface of the composite film is uneven, and further certain influence is exerted on the performance of the battery, and the problems that in the prior art, inorganic materials are directly coated on the diaphragm through a coating method to cause uneven coating or dispersion, and further the performance of the prepared diaphragm is reduced at different positions, and further the diaphragm is easily damaged by high-temperature melting or external force tearing in severe environments are solved.
The diaphragm prepared by the invention contains a large amount of amino groups, and the surface of the surface amination nano ceramic powder also contains a large amount of amino groups, under the crosslinking action of hexamethylene diisocyanate, the surface amination nano ceramic powder is crosslinked and fixed on the high-strength microporous polyurethane film, so that the nano ceramic powder shields micropores on the microporous polyurethane film, the aperture of the polyurethane film is further reduced, the short circuit caused by contact of the anode and the cathode of the battery due to overlarge aperture is prevented, the aperture is uniformly dispersed, and the problem that the short circuit is caused by large local aperture due to nonuniform aperture of the diaphragm in the diaphragm prepared by a coating or dipping method in the prior art is solved.
Each polymer monomer prepared by the method contains two sulfonic acid groups, and each polymer monomer contains-C-conjugated group, so that the polymerized polyurethane contains a large number of sulfonic acid groups and-C-conjugated group, and the polyurethane has super-hydrophilicity due to the fact that the sulfonic acid groups have high hydrophilic capacity, and the polyurethane has high mechanical strength, thermal stability and high hydrophilicity under the action of the-C-conjugated group, so that the problems that hydrophilic wettability and high mechanical performance cannot be simultaneously realized by an existing composite membrane preparation matrix are solved.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a structural formula of the reaction of 1, 5-naphthalene disulfonyl chloride of the present invention;
FIG. 2 is a reaction scheme of a cross-linked dicarboxylic polymeric monomer according to the present invention;
FIG. 3 is a reaction structure of high-strength super-hydrophilic polyurethane;
FIG. 4 is a reaction structure of the composite polymer diaphragm.
Detailed Description
Referring to FIGS. 1-4, the following embodiments are illustrated in detail:
example 1:
the specific preparation process of the high-strength super-hydrophilic polyurethane comprises the following steps:
weighing 1, 5-naphthalenedisulfonic acid disodium salt of 1kg, dissolving in 7L water, heating to 80 ℃, adding thionyl chloride of 2.9kg, carrying out reflux reaction for 5h, separating liquid, retaining a water phase, and carrying out evaporative crystallization on the water phase to obtain 1, 5-naphthalenedisulfonyl chloride;
weighing 1kg of glutamic acid, dissolving the glutamic acid in 15L of 1% dilute hydrochloric acid by mass fraction to prepare a glutamic acid solution, adding the prepared glutamic acid solution into a reaction container, heating to 70 ℃, simultaneously adding 0.73kg of 1, 5-naphthalene disulfonyl chloride prepared in the step I into the reaction container, reacting for 3 hours at a constant temperature, evaporating and crystallizing, washing crystals by using an acetone solution, and drying to obtain a cross-linked dicarboxyl polymeric monomer;
dissolving 1kg of cross-linked dicarboxyl polymerization monomer prepared in the step III in water, adding the monomer into a reaction container, adding a certain amount of 0.06kg of dodecyl mercaptan, uniformly mixing, heating to 120 ℃, dropwise adding 2.5L of ethylenediamine solution into the reaction container, controlling the temperature to rise while dropwise adding, controlling the dropwise adding speed to be 10-11mL per minute, controlling the temperature to rise by 30 ℃ per hour, stopping heating until the temperature rises to 260 ℃, then carrying out constant-temperature reaction for 1-1.5h, cooling to 70 ℃, and discharging to obtain the high-strength super-hydrophilic polyurethane.
The specific preparation process of the aminated nano ceramic powder comprises the following steps: weighing 1kg of nano ceramic powder, adding the nano ceramic powder into 13L of water, uniformly dispersing by ultrasonic, adding 0.53kg of ethylenediamine, uniformly stirring and mixing, dropwise adding 1.21kg of bisphenol A epoxy resin liquid, violently stirring while dropwise adding, reacting at constant temperature for 1h after completely dropwise adding, and then filtering and washing to obtain the surface amination nano ceramic powder.
Example 2:
the specific preparation process of the high-strength super-hydrophilic polyurethane comprises the following steps:
weighing 1, 5-naphthalenedisulfonic acid disodium salt of 1kg, dissolving in 8L water, heating to 80 ℃, adding 3kg of thionyl chloride, carrying out reflux reaction for 5h, separating liquid, retaining a water phase, and carrying out evaporative crystallization on the water phase to obtain 1, 5-naphthalenedisulfonyl chloride;
weighing 1kg of glutamic acid, dissolving the glutamic acid in 15L of 1% dilute hydrochloric acid by mass fraction to prepare a glutamic acid solution, adding the prepared glutamic acid solution into a reaction container, heating to 70 ℃, simultaneously adding 0.75kg of 1, 5-naphthalene disulfonyl chloride prepared in the step I into the reaction container, reacting for 3 hours at a constant temperature, evaporating and crystallizing, washing crystals by using an acetone solution, and drying to obtain a cross-linked dicarboxyl polymeric monomer;
dissolving 1kg of cross-linked dicarboxyl polymerization monomer prepared in the step III in water, adding the monomer into a reaction container, adding a certain amount of 0.06kg of dodecyl mercaptan, uniformly mixing, heating to 120 ℃, dropwise adding 2.6L of ethylenediamine solution into the reaction container, controlling the temperature to rise while dropwise adding, controlling the dropwise adding speed to be 10-11mL per minute, controlling the temperature to rise by 30 ℃ per hour, stopping heating until the temperature rises to 260 ℃, then carrying out constant-temperature reaction for 1-1.5h, cooling to 70 ℃, and discharging to obtain the high-strength super-hydrophilic polyurethane.
The specific preparation process of the aminated nano ceramic powder comprises the following steps: weighing 1kg of nano ceramic powder, adding the nano ceramic powder into 13L of water, uniformly dispersing by ultrasonic, adding 0.55kg of ethylenediamine, uniformly stirring and mixing, dropwise adding 1.25kg of bisphenol A epoxy resin liquid, violently stirring while dropwise adding, reacting at constant temperature for 1h after completely dropwise adding, and then filtering and washing to obtain the surface amination nano ceramic powder.
Example 3:
a preparation process of a composite polymer diaphragm for a lithium battery comprises the following preparation processes:
firstly, adding the high-strength super-hydrophilic polyurethane prepared in the example 1 into an extruder, melting the polyurethane at 150 ℃, extruding the polyurethane, stretching the polyurethane to form a parallel flaky crystal structure, separating the flaky crystal structure by heat treatment and stretching the flaky crystal structure again to form elongated micropores, and finally performing heat setting to obtain a high-strength microporous polyurethane membrane;
and secondly, dissolving 0.215kg of the surface aminated nano ceramic powder prepared in the example 1 in 1.505L of water, ultrasonically dispersing the powder uniformly, then soaking 100g of the high-strength microporous polyurethane film prepared in the first step in the water, ultrasonically oscillating the solution for 30min, then dropwise adding 0.136kg of hexamethylene diisocyanate into the solution while dropwise adding the hexamethylene diisocyanate, carrying out ultrasonic reaction for 2h after the dropwise adding is completed, then taking out the high-strength microporous polyurethane film, and washing and drying the film by using ethanol to obtain the composite polymer diaphragm.
Example 4:
a preparation process of a composite polymer diaphragm for a lithium battery comprises the following preparation processes:
firstly, adding the high-strength super-hydrophilic polyurethane prepared in the example 2 into an extruder, melting the polyurethane at 150 ℃, extruding the polyurethane, stretching the polyurethane to form a parallel flaky crystal structure, separating the sheets by heat treatment and stretching the crystal structure again to form elongated micropores, and finally performing heat setting to obtain a high-strength microporous polyurethane membrane;
and secondly, dissolving 0.218kg of the surface aminated nano ceramic powder prepared in the embodiment 2 in 1.526L of water, ultrasonically dispersing the powder uniformly, then soaking 100g of the high-strength microporous polyurethane membrane prepared in the first step in the water, ultrasonically oscillating the membrane for 30min, then dropwise adding 0.138kg of hexamethylene diisocyanate into the membrane, carrying out ultrasonic treatment while dropwise adding the hexamethylene diisocyanate, carrying out ultrasonic reaction for 2h after the dropwise adding is completed, then taking out the high-strength microporous polyurethane membrane, and washing and drying the membrane by using ethanol to obtain the composite polymer diaphragm.
Example 5:
a preparation process of a composite polymer diaphragm for a lithium battery comprises the following preparation processes:
firstly, adding a certain amount of polyurethane into an extruder, melting at 150 ℃, then extruding, stretching to form a parallel-arranged flaky crystal structure, then separating sheet layers through heat treatment and stretching again to form elongated micropores, and finally performing heat setting to obtain a polyurethane film;
and secondly, dissolving 0.218kg of the surface amination nano ceramic powder prepared in the embodiment 2 in 1.526L of water, ultrasonically dispersing the nano ceramic powder uniformly, then soaking 100g of the polyurethane film prepared in the first step in the water, ultrasonically oscillating the polyurethane film for 30min, then dropwise adding 0.138kg of hexamethylene diisocyanate while dropwise adding the hexamethylene diisocyanate, ultrasonically reacting the polyurethane film for 2h after the dropwise adding is completed, then taking out the high-strength microporous polyurethane film, and washing and drying the polyurethane film by using ethanol to obtain the composite polymer diaphragm.
Example 6:
a preparation process of a composite polymer diaphragm for a lithium battery comprises the following preparation processes:
firstly, adding the high-strength super-hydrophilic polyurethane prepared in the example 2 into an extruder, melting the polyurethane at 150 ℃, extruding the polyurethane, stretching the polyurethane to form a parallel flaky crystal structure, separating the sheets by heat treatment and stretching the crystal structure again to form elongated micropores, and finally performing heat setting to obtain a high-strength microporous polyurethane membrane;
and secondly, adding 0.218kg of nano ceramic powder into a polyvinyl alcohol solution, uniformly mixing, soaking the high-strength microporous polyurethane membrane prepared in the first step in the prepared mixed solution for 2-3min, and then taking out and drying to obtain the composite polymer diaphragm.
Example 7:
firstly, adding polyurethane into an extruder, melting at 150 ℃, then extruding, stretching to form a parallel flaky crystal structure, then separating sheet layers through heat treatment and stretching again to form elongated micropores, and finally performing heat setting to obtain a polyurethane film;
and secondly, adding 0.218kg of nano ceramic powder into a polyvinyl alcohol solution, uniformly mixing, soaking the polyurethane film prepared in the first step in the prepared mixed solution for 2-3min, and then taking out and drying to obtain the composite polymer diaphragm.
Example 8:
the composite polymer membranes prepared in examples 3 to 7 were subjected to mechanical property measurements at 3 different positions, and the specific measurement results are shown in table 1:
table 1: tensile strength (MPa) of composite polymer diaphragm at different positions
| Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| 1 | 59.32 | 59.36 | 52.16 | 61.35 | 56.38 |
| 2 | 59.31 | 59.34 | 52.13 | 48.11 | 51.39 |
| 3 | 59.32 | 59.35 | 52.14 | 53.29 | 43.53 |
As can be seen from table 1, since the nano ceramic powder is fixed on the surface of the polyurethane film by chemical crosslinking, not only the bonding ability is strong, and the nano ceramic powder is not separated under the action of external force and high temperature, but also the ceramic powder fixed by chemical crosslinking is uniformly distributed, compared with the ceramic powder directly fixed by bonding, since the ceramic powder has higher strength and high temperature resistance, the high temperature resistance and strength of the prepared composite film can be improved by fixing a layer of ceramic powder on both surfaces of the composite film, and since the sleeve system powder is uniformly distributed, the high temperature resistance and strength of the composite film are prevented from being uniformly distributed when the ceramic powder is directly fixed by bonding through the adhesive in the conventional technology, and the high temperature resistance and strength at different positions of the prepared composite film; meanwhile, compared with the polyurethane film directly prepared from the existing polyurethane resin, the polyurethane film prepared from the crosslinked dicarboxyl polymerization monomer crosslinked by the 1, 5-naphthalene disulfonyl chloride contains a conjugated group, so that the strength and the high temperature resistance of the composite film can be further improved, and the short circuit inside the lithium battery caused by the damage of the composite film under the action of external force is prevented.
Example 9:
the composite films prepared in examples 3 to 7 were cut into samples having the same size in area, the composite films were dried at 100 ℃ and weighed m0Soaking the composite membrane in electrolyte for 2h, taking out, sucking the electrolyte on the surface of the composite membrane with filter paper, weighing, and counting as m1(ii) a Calculating the electrolyte absorptivity of the composite membrane as follows:
table 2: electrolyte absorptivity of composite membranes prepared in examples 3 to 7
As can be seen from Table 2, the sulfonic group contained in the polyurethane membrane prepared from the crosslinked dicarboxyl polymerized monomer crosslinked by 1, 5-naphthalene disulfonyl chloride can play a stronger hydrophilic role, so that the liquid absorption capacity of the composite membrane is improved, and the penetration capacity of the electrolyte can be guaranteed.
Example 10:
the heat shrinkage performance of the composite films prepared in examples 3 to 7 was investigated, and the results are shown in Table 3:
table 3: results of measuring Heat shrinkage Properties of composite films prepared in examples 3 to 7
As can be seen from Table 3, the polyurethane film prepared from the crosslinked dicarboxyl polymeric monomer crosslinked by 1, 5-naphthalene disulfonyl chloride contains conjugated groups, and the nano ceramic powder is uniformly distributed on the surface of the prepared composite film, so that the high-temperature resistance of the composite film can be improved, and the composite diaphragm is free from pinholes or damage at high temperature, thereby causing short circuit inside the battery.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A preparation process of a composite polymer diaphragm for a lithium battery is characterized by comprising the following preparation processes:
the first step is to prepare the high-strength super-hydrophilic polyurethane, and the specific preparation method comprises the following steps: weighing a certain amount of 1, 5-naphthalenedisulfonic acid disodium salt, dissolving in water, heating to 80 ℃, adding thionyl chloride, performing reflux reaction for 5 hours, separating liquid, retaining a water phase, and performing evaporative crystallization on the water phase to obtain 1, 5-naphthalenedisulfonic acid chloride;
weighing a certain amount of glutamic acid, dissolving the glutamic acid in 1% dilute hydrochloric acid by mass fraction to prepare a glutamic acid solution, adding the prepared glutamic acid solution into a reaction container, heating to 70 ℃, simultaneously adding the 1, 5-naphthalene disulfonyl chloride prepared in the step I into the reaction container, reacting for 3 hours at a constant temperature, evaporating and crystallizing, simultaneously washing crystals by using an acetone solution, and drying to obtain a cross-linked dicarboxy polymerization monomer;
dissolving the cross-linked dicarboxyl polymerization monomer prepared in the step II in water, adding the monomer into a reaction container, adding a certain amount of molecular weight regulator, uniformly mixing, heating to 120 ℃, dropwise adding an ethylenediamine solution into the monomer while controlling the temperature to rise, controlling the dropping speed to be 10-11mL per minute, controlling the temperature to rise by 30 ℃ per hour, stopping heating until the temperature rises to 260 ℃, then carrying out constant temperature reaction for 1-1.5h, cooling to 70 ℃, and discharging to obtain the high-strength super-hydrophilic polyurethane;
secondly, adding the high-strength super-hydrophilic polyurethane prepared in the first step into an extruder, melting the polyurethane at 150 ℃, extruding the polyurethane, stretching the polyurethane to form a parallel flaky crystal structure, separating the sheets by heat treatment and stretching the crystal layer again to form elongated micropores, and finally performing heat setting to obtain the high-strength microporous polyurethane membrane;
and thirdly, dissolving the prepared surface amination nano ceramic powder in water, uniformly dispersing by using ultrasonic waves, soaking the high-strength microporous polyurethane membrane prepared in the second step in water, performing ultrasonic oscillation for 30min, dropwise adding hexamethylene diisocyanate while performing ultrasonic reaction for 2h after complete dropwise addition, taking out the high-strength microporous polyurethane membrane, washing by using ethanol, and drying to obtain the composite polymer diaphragm.
2. The preparation process of the composite polymer diaphragm for the lithium battery as claimed in claim 1, wherein in the preparation process of the high-strength super-hydrophilic polyurethane, 7-8mL of water and 2.9-3g of thionyl chloride are added into each gram of 1, 5-sodium naphthalenedisulfonate.
3. The preparation process of the composite polymer diaphragm for the lithium battery as claimed in claim 1, wherein 15mL of dilute hydrochloric acid with the mass fraction of 1% is added into every gram of glutamic acid in the preparation process of the high-strength super-hydrophilic polyurethane, and 0.73-0.75g of 1, 5-naphthalene disulfonyl chloride is added.
4. The process of claim 1, wherein 0.06g of molecular weight regulator and 2.5-2.6mL of ethylenediamine are added to each gram of cross-linked dicarboxy polymerization monomer in the step III of the preparation of the high-strength super-hydrophilic polyurethane, wherein the molecular weight regulator is dodecyl mercaptan.
5. The process of claim 1, wherein the surface-aminated nano-ceramic powder is prepared by the following steps: weighing a certain amount of nano ceramic powder, adding the nano ceramic powder into water, uniformly dispersing by using ultrasonic waves, adding a certain amount of ethylenediamine into the nano ceramic powder, uniformly stirring and mixing, dropwise adding bisphenol A epoxy resin liquid into the nano ceramic powder while violently stirring, reacting at constant temperature for 1h after complete dropwise addition, and then filtering and washing to obtain the surface aminated nano ceramic powder.
6. The process of claim 5, wherein each gram of nano ceramic powder is added with 13mL of water, 0.53-0.55g of ethylenediamine and 1.21-1.25g of bisphenol A epoxy resin solution.
7. The process of claim 1, wherein in the third step, 7mL of water is added to each gram of the surface aminated nano ceramic powder, 2.15-2.18g of the surface aminated nano ceramic powder is added to each gram of the high-strength microporous polyurethane film, and 1.36-1.38g of hexamethylene diisocyanate is added to each gram of the high-strength microporous polyurethane film.
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| CN103956451A (en) * | 2014-05-16 | 2014-07-30 | 中国东方电气集团有限公司 | Composite ceramic membrane for lithium ion batteries and preparation method thereof |
| CN106953049A (en) * | 2017-01-20 | 2017-07-14 | 东莞市卓高电子科技有限公司 | A kind of preparation method of the ceramic coating membrane of high security |
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| US6521686B1 (en) * | 1999-01-20 | 2003-02-18 | Siemens Aktiengesellschaft | Aqueous ceramic casting material, method for producing said casting material and use of the same |
| CN103956451A (en) * | 2014-05-16 | 2014-07-30 | 中国东方电气集团有限公司 | Composite ceramic membrane for lithium ion batteries and preparation method thereof |
| CN106953049A (en) * | 2017-01-20 | 2017-07-14 | 东莞市卓高电子科技有限公司 | A kind of preparation method of the ceramic coating membrane of high security |
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