CN109873107B - Preparation process of new energy lithium ion battery diaphragm - Google Patents
Preparation process of new energy lithium ion battery diaphragm Download PDFInfo
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- CN109873107B CN109873107B CN201910205183.3A CN201910205183A CN109873107B CN 109873107 B CN109873107 B CN 109873107B CN 201910205183 A CN201910205183 A CN 201910205183A CN 109873107 B CN109873107 B CN 109873107B
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Abstract
The invention discloses a preparation process of a new energy lithium ion battery diaphragm, which comprises the following specific preparation processes: adding polyethylene and high liquid absorption polymer into a stirring kettle simultaneously, adding dimethyl phthalate and polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and melting the two polymers into a molten state to obtain a casting solution; pouring the casting solution prepared in the first step into a mold, and vulcanizing a heated flat plate to form a film; and soaking the prepared porous membrane in a liquid-absorbing foaming solution, taking out, foaming and curing to obtain the battery diaphragm. According to the invention, the porous membrane is prepared by fusing polyethylene and the high liquid absorption polymer, and then the foaming membrane is compounded on the surface and the bottom surface of the porous membrane, so that the diaphragm forms a three-layer sandwich structure, the central membrane has higher liquid absorption and retention capacity, the liquid absorption and retention performances of the two-layer cellular porous liquid absorption membrane are greatly enhanced, and the liquid retention performance of the central membrane can be improved and the mechanical strength of the diaphragm is also improved through the three-layer sandwich structure.
Description
Technical Field
The invention belongs to the field of lithium ion battery preparation, and relates to a preparation process of a new energy lithium ion battery diaphragm.
Background
The diaphragm is used as one of important components of the lithium battery, lithium ions can pass through the diaphragm and simultaneously block the positive electrode and the negative electrode, short circuit is prevented, meanwhile, the absorption of electrolyte is influenced by the height of the liquid absorption performance of the diaphragm, the diaphragm is used as an ion channel, the passing of the electrolyte must be ensured, meanwhile, the mechanical performance of the diaphragm determines whether the diaphragm is damaged under severe environment, and meanwhile, the liquid absorption and retention performance and the ionic conductivity of the diaphragm are improved;
the diaphragm prepared by the prior art is usually prepared by using a polyethylene material, and the obtained diaphragm has high mechanical properties, but has low liquid absorption and retention properties, and meanwhile, the polyethylene material has poor thermal stability at high temperature, so that the diaphragm cannot meet the requirements.
Disclosure of Invention
The invention aims to provide a preparation process of a new energy lithium ion battery diaphragm, which is characterized in that polyethylene and a high liquid absorption polymer are fused to prepare a porous membrane, and then a foaming membrane is compounded on the surface and the bottom surface of the porous membrane, so that the diaphragm is composed of a high liquid absorption central membrane and two layers of cellular porous liquid absorption membranes; because high imbibition polymer itself has higher imbibition performance, make the center film have higher imbibition and protect liquid ability, form a large amount of bubbles after foaming simultaneously and increased specific surface area, and then increased the imbibition area, make the imbibition and protect liquid ability of two-layer cellular imbibition film strengthen greatly, through three-layer sandwich structure, can improve the liquid ability of keeping of center film, and three-layer structure has also improved the mechanical strength of diaphragm simultaneously, breaking strength reaches 52.13MPa, imbibition rate reaches 286.31% simultaneously, it reaches 92.23% to keep the liquid ability, and then improve the cycle life of lithium cell, the lower problem of current lithium cell diaphragm imbibition and the liquid ability of keeping is solved.
The purpose of the invention can be realized by the following technical scheme:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
firstly, adding polyethylene and a high liquid absorption polymer into a stirring kettle simultaneously, then adding dimethyl phthalate and polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and smelting the two polymers into a molten state to obtain a casting solution; wherein the mass ratio of the polyethylene to the high liquid absorption polymer is 1: 3.2 to 3.3, wherein the total mass of the polyethylene and the high liquid absorption polymer added in each kilogram of dimethyl phthalate is 295-302g, and the mass of the polyethylene glycol added in is 134-138 g;
wherein the preparation process of the high liquid absorption polymer is as follows:
weighing a certain amount of melamine, dissolving the melamine in methanol, heating to 70-75 ℃, adding trimethylolpropane triglycidyl ether, reacting at constant temperature for 1h, adding 2, 3-epoxypropyltrimethylammonium chloride, reacting at constant temperature under reflux for 8-9h, evaporating to remove the solvent methanol to obtain a polymer, and washing and drying the polymer by deionized water to obtain the polymer; the melamine ring contains three amino groups which can carry out ring-opening polymerization reaction with epoxy groups in trimethylolpropane triglycidyl ether, the three amino groups are uniformly distributed in different directions on the ring, meanwhile, the three epoxy groups in the trimethylolpropane triglycidyl ether are also uniformly distributed in three different directions, an irregular hyperbranched structure is formed in the polymerization process, 2, 3-epoxypropyltrimethylammonium chloride is added in the polymerization process, the epoxy groups in the 2, 3-epoxypropyltrimethylammonium chloride also react with unreacted amino groups in melamine, so that ammonium chloride groups are introduced into a polymer skeleton, and meanwhile, the ammonium chloride has higher hydrophilic performance, so that the hydrophilic moisture absorption performance of the prepared polymer is enhanced; meanwhile, the prepared polymer is polymerized by melamine monomer, so that the polymer has higher corrosion resistance and heat resistance; wherein the mol ratio of melamine to trimethylolpropane triglycidyl ether is 1: 0.73-0.76, and the molar ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.28-0.29;
secondly, adding the polymer prepared in the first step into acetone, adding sodium hydroxyethyl sulfonate into the acetone, heating to 50-60 ℃, stirring and mixing for 3-5min, then dropwise adding toluene diisocyanate into the acetone, stirring and reacting for 6-7h at constant temperature after complete dropwise addition, and then filtering and washing to obtain a high liquid absorption polymer; wherein 1.49-1.51g of hydroxyethyl sodium sulfonate is added into each gram of polymer, and 1.79-1.82g of toluene diisocyanate is added at the same time; because the prepared polymer is polymerized by the ring-opening reaction of the amino and the epoxy group, and hydroxyl is generated after the amino and the epoxy group are subjected to ring opening, the hydroxyl and the hydroxyl in the hydroxyethyl sodium sulfonate can react with isocyanate groups in the toluene diisocyanate to graft the hydroxyethyl sodium sulfonate on a polymer skeleton, so that sulfonate ions are introduced into the polymer, and the liquid absorption performance of the polymer is improved;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film;
and thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, taking out the porous membrane, and then foaming and curing the porous membrane at the temperature of 80-85 ℃ for 5-6h to obtain the battery diaphragm.
The preparation process of the imbibed foaming solution is as follows: adding the prepared high liquid absorption polymer into isopropyl acetate, stirring for dissolving, then adding hydroxyl silicone oil into the mixture, stirring and mixing uniformly, then adding n-pentane and tween 80 into the mixture, adding a sulfuric acid solution with the concentration of 20% into the mixture after mixing uniformly, and stirring and mixing uniformly at the temperature of 25-30 ℃ to obtain a liquid absorption foaming solution, wherein 8-10mL of isopropyl acetate is added into each gram of high liquid absorption polymer, 0.21-0.23g of hydroxyl silicone oil is added, 0.09-0.1g of tween 80 is added, 0.09-0.11g of n-pentane is added, and 0.11-0.13g of 20% sulfuric acid solution is added; because imbibition foaming solution itself contains higher imbibition performance, form the cell structure on the surface of porous membrane after the foaming, not only can not cause the jam in porous membrane space, improve the bubble quantity simultaneously, and then increase specific surface area, improve imbibition water retention property, and the hydroxyl silicone oil that contains among the expanded material, can improve the corrosion resisting property and the thermal stability of diaphragm, directly foam through the both sides at the porous membrane simultaneously, because porous membrane itself has higher imbibition water retention property, and two-layer foaming membrane all has higher imbibition water retention property, and then make the diaphragm of preparation have stronger inside and the surface all has higher imbibition water retention property.
The invention has the beneficial effects that:
the invention prepares the porous membrane by fusing polyethylene and high liquid absorption polymer, and then compounds the foaming membrane on the surface and the bottom surface of the porous membrane, so that the diaphragm is composed of a high liquid absorption central membrane and two layers of cellular porous liquid absorption membranes; because high imbibition polymer itself has higher imbibition performance, make the center film have higher imbibition and protect liquid ability, form a large amount of bubbles after foaming simultaneously and increased specific surface area, and then increased the imbibition area, make the imbibition and protect liquid performance of two-layer cellular imbibition film strengthen greatly, through three-layer sandwich structure, can improve the protect liquid performance of center film, and three-layer structure has also improved the mechanical strength of diaphragm simultaneously, breaking strength reaches 52.13MPa, imbibition rate reaches 286.31% simultaneously, it reaches 92.23% to protect liquid rate, and then improve the cycle life of lithium cell.
According to the invention, when the high liquid absorption polymer is prepared, a melamine ring and trimethylolpropane triglycidyl ether are polymerized to generate a hyperbranched polymer, 2, 3-epoxypropyltrimethylammonium chloride is added in the polymerization process, and an epoxy group in the 2, 3-epoxypropyltrimethylammonium chloride also reacts with unreacted amino in melamine, so that an ammonium chloride group is introduced into a polymer skeleton, and meanwhile, the hydrophilic moisture absorption performance of the prepared polymer is enhanced because the ammonium chloride has higher hydrophilic performance; meanwhile, the prepared polymer is polymerized through the ring-opening reaction of the amino and the epoxy group, and hydroxyl is generated after the amino and the epoxy group are subjected to ring opening, so that the hydroxyl and the hydroxyl in the hydroxyethyl sodium sulfonate can react with isocyanate groups in the toluene diisocyanate to graft the hydroxyethyl sodium sulfonate on a polymer skeleton, so that sulfonate ions are introduced into the polymer, and the liquid absorption performance of the polymer is further improved.
According to the invention, the hydroxyl silicone oil is added in the preparation process of the imbibing foaming solution, so that the surface foaming film contains a large number of siloxane bonds, the high temperature resistance of the foaming film is further improved, the high temperature resistance of the whole isolating film is realized through the barrier effect of the foaming film, and the problems that the existing polyethylene material is poor in thermal stability and cannot meet the requirements are solved.
Detailed Description
Example 1:
the preparation process of the high liquid absorption polymer is as follows:
weighing 1.26kg of melamine to dissolve in 12L of methanol, heating to 70-75 ℃, adding 2.2kg of trimethylolpropane triglycidyl ether, reacting at constant temperature for 1h, adding 0.42kg of 2, 3-epoxypropyl trimethyl ammonium chloride, reacting at constant temperature for 8-9h, and evaporating to remove the solvent methanol to obtain a polymer;
adding 1kg of the polymer prepared in the first step into 12L of acetone, adding 1.49kg of sodium hydroxyethyl sulfonate, heating to 50-60 ℃, stirring and mixing for 3-5min, then dropwise adding 1.79kg of toluene diisocyanate, stirring and reacting at constant temperature for 6-7h after complete dropwise addition, and then filtering and washing to obtain the high liquid absorption polymer.
Example 2:
the preparation process of the high liquid absorption polymer is as follows: weighing 1.26kg of melamine to dissolve in 12L of methanol, heating to 70-75 ℃, adding 2.2kg of trimethylolpropane triglycidyl ether, reacting at constant temperature for 1h, adding 0.42kg of 2, 3-epoxypropyltrimethylammonium chloride, reacting at constant temperature for 8-9h, and evaporating to remove the solvent methanol to obtain the polymer.
Example 3:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, adding 1kg of polyethylene and 3.2kg of the high liquid absorption polymer prepared in example 1 into a stirring kettle at the same time, then adding 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and then melting both polymers into a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining a porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at 80-85 ℃ for 5-6h to obtain the battery diaphragm; the preparation process of the imbibed foaming solution is as follows: 1kg of the high liquid absorbent polymer prepared in example 1 was added to 8L of isopropyl acetate, dissolved by stirring, then 0.21kg of hydroxy silicone oil was added thereto, mixed by stirring uniformly, then 0.09kg of n-pentane and 0.09kg of Tween 80 were added thereto, after mixing uniformly, 0.11kg of a 20% sulfuric acid solution was added thereto, and mixed by stirring uniformly at a controlled temperature of 25 to 30 ℃ to obtain a liquid absorbent foamed solution.
Example 4:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, adding 1kg of polyethylene and 3.2kg of the high liquid absorption polymer prepared in example 1 into a stirring kettle at the same time, then adding 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and then melting both polymers into a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at the temperature of 80-85 ℃ for 5-6h to obtain a battery diaphragm; the preparation process of the imbibed foaming solution is as follows: 1kg of the high liquid absorbing polymer prepared in example 2 was added to 8L of isopropyl acetate, dissolved by stirring, then 0.21kg of hydroxy silicone oil was added thereto, mixed by stirring uniformly, then 0.09kg of n-pentane and 0.09kg of Tween 80 were added thereto, after mixing uniformly, 0.11kg of a 20% sulfuric acid solution was added thereto, and mixed by stirring uniformly at a controlled temperature of 25 to 30 ℃ to obtain a liquid absorbing foamed solution.
Example 5:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, 1kg of polyethylene and 3.2kg of the high liquid absorption polymer prepared in example 2 were added to a stirred tank at the same time, then 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol were added thereto, the temperature was raised to 200 ℃, stirred and mixed uniformly, and at this time both polymers were melted to a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at 80-85 ℃ for 5-6h to obtain the battery diaphragm; the preparation process of the imbibed foaming solution is as follows: 1kg of the high liquid absorbing polymer prepared in example 2 was added to 8L of isopropyl acetate, dissolved by stirring, then 0.21kg of hydroxy silicone oil was added thereto, mixed by stirring uniformly, then 0.09kg of n-pentane and 0.09kg of Tween 80 were added thereto, after mixing uniformly, 0.11kg of a 20% sulfuric acid solution was added thereto, and mixed by stirring uniformly at a controlled temperature of 25 to 30 ℃ to obtain a liquid absorbing foamed solution.
Example 6:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, adding 4kg of polyethylene into a stirring kettle, then adding 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and smelting two polymers into a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at 80-85 ℃ for 5-6h to obtain the battery diaphragm; the preparation process of the imbibed foaming solution is as follows: 1kg of the high liquid absorbent polymer prepared in example 1 was added to 8L of isopropyl acetate and dissolved with stirring, then 0.21kg of hydroxysilicone oil was added thereto and mixed well with stirring, then 0.09kg of n-pentane and 0.09kg of Tween 80 were added thereto, after mixing well, 0.11kg of a 20% strength sulfuric acid solution was added thereto and mixed well with stirring at a controlled temperature of 25-30 ℃ to obtain a liquid absorbent foamed solution.
Example 7:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, adding 4kg of the high liquid absorption polymer prepared in example 1 into a stirring kettle, adding 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol, heating to 200 ℃, stirring and mixing uniformly, and smelting the two polymers into a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at the temperature of 80-85 ℃ for 5-6h to obtain a battery diaphragm; wherein the preparation process of the imbibed foaming solution is as follows: 1kg of the high liquid absorbent polymer prepared in example 1 was added to 8L of isopropyl acetate, dissolved by stirring, then 0.21kg of hydroxy silicone oil was added thereto, mixed by stirring uniformly, then 0.09kg of n-pentane and 0.09kg of Tween 80 were added thereto, after mixing uniformly, 0.11kg of a 20% sulfuric acid solution was added thereto, and mixed by stirring uniformly at a controlled temperature of 25 to 30 ℃ to obtain a liquid absorbent foamed solution.
Example 8:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, 1kg of polyethylene and 3.2kg of the high liquid absorption polymer prepared in example 1 were added to a stirred tank at the same time, then 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol were added thereto, the temperature was raised to 200 ℃, stirred and mixed uniformly, and at this time both polymers were melted to a molten state to obtain a casting solution;
and secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath to rapidly cool and solidify, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film, namely the battery diaphragm.
Example 9:
a preparation process of a new energy lithium ion battery diaphragm comprises the following specific preparation processes:
step one, adding 1kg of polyethylene and 3.2kg of the high liquid absorption polymer prepared in example 2 into a stirring kettle at the same time, then adding 14.24kg of dimethyl phthalate and 1.91kg of polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and then melting both polymers into a molten state to obtain a casting solution;
and secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath to rapidly cool and solidify, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol by solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol, and obtaining the porous composite film, namely the battery diaphragm.
Example 10:
the separators prepared in examples 3 to 9 were subjected to the following specific measurement procedures:
(1) and (3) measuring mechanical properties: because the lithium battery has certain mechanical property, the safety in the use process can be ensured, the mechanical property of the isolating membrane is measured by an electronic tensile testing machine, and the isolating membrane is cut into samples of 20mm multiplied by 150mm to be measured during the test.
(2) And (3) measuring the liquid absorption rate of the electrolyte: cutting the diaphragm into 40mm × 40mm samples, and heating the samples at 80-90 deg.CDried for 2h, cooled and weighed as m 0 Then immersing the diaphragm into electrolyte, taking out after immersing for 2h, wherein the electrolyte is prepared by adding 1g ethylene carbonate and 1g dimethyl carbonate into 1mol lithium hexafluorophosphate, completely absorbing the redundant electrolyte on the surface of the diaphragm by using filter paper, weighing the residual electrolyte as m 1 Wherein the liquid absorption rate P is (m) 1 -m 0 )/m 0 ×100％。
(3) Liquid retention determination: cutting the diaphragm into 40mm × 40mm samples, drying the samples at 80-90 deg.C for 2h, cooling, weighing and recording as m 0 Then immersing the diaphragm into electrolyte, taking out after soaking for 2h, wherein the electrolyte is prepared by adding 1g ethylene carbonate and 1g dimethyl carbonate into 1mol lithium hexafluorophosphate, then placing the diaphragm between two layers of filter paper, placing a weight with the weight of 100g on the surface of the upper layer of filter paper, and measuring the mass of the diaphragm as m after pressing for 30s 1 Wherein the liquid retention rate R is (m) 1 -m 0 )/m 0 X 100%; the structure of the separator for measuring the above properties is shown in table 1:
table 1: results of performance measurement of the separators prepared in examples 3 to 8:
as can be seen from table 1, the strength of the separator prepared in example 3 reaches 52.13MPa, the liquid absorption rate reaches 286.31%, and the liquid retention rate reaches 92.23%, while the high liquid absorbent polymer prepared in example 1 is replaced with the high liquid absorbent polymer prepared in example 2 in examples 4 and 5, so that the breaking strength, the liquid absorption rate and the liquid retention rate are all reduced, and since no polymerized grafted sodium sulfonate group is present in the preparation process of the polymer in example 2, the content of the liquid absorption group in the polymer is reduced, and since the polymerization degree of the polymer is improved by the graft fixation with the polymer when the sodium sulfonate is polymerized, the breaking strength of the polymer is improved; the high liquid absorption polymer is not added when the porous membrane is prepared in the embodiment 6, the polyethylene polymer is directly used, the liquid absorption and water retention performance of the porous membrane is greatly reduced, but the mechanical strength of the porous membrane is enhanced, the high liquid absorption polymer is completely used in the embodiment 7 without the polyethylene polymer, so that the mechanical strength of the isolating membrane is reduced, meanwhile, the absorbing area of the isolating membrane is greatly reduced for the foaming membrane which is not compounded on the surface of the porous membrane in the embodiments 8 and 9, and the breaking strength, the liquid absorption rate and the liquid retention rate of the isolating membrane are all reduced to a great extent.
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 (6)
1. The preparation process of the new energy lithium ion battery diaphragm is characterized by comprising the following specific preparation processes:
firstly, adding polyethylene and a high liquid absorption polymer into a stirring kettle simultaneously, then adding dimethyl phthalate and polyethylene glycol into the stirring kettle, heating to 200 ℃, stirring and mixing uniformly, and smelting the two polymers into a molten state to obtain a casting solution;
secondly, pouring the casting solution prepared in the first step into a mold, vulcanizing a heating flat plate to form a film, then moving the mold into a cooling bath for rapid cooling and solidification, then taking out the solidified film, soaking the solidified film in ethanol for 24-26h, removing dimethyl phthalate and polyethylene glycol in the solidified film through solvent replacement, finally drying the soaked composite film in a drying chamber at 50-60 ℃, removing the replaced ethanol in the composite film, and obtaining a porous composite film;
thirdly, soaking the porous membrane prepared in the second step in the liquid-absorbing foaming solution for 1-2min, then fishing out the porous membrane, and then foaming and curing the porous membrane at 80-85 ℃ for 5-6h to obtain the battery diaphragm;
the preparation process of the high liquid absorption polymer is as follows:
weighing a certain amount of melamine, dissolving the melamine in methanol, heating to 70-75 ℃, adding trimethylolpropane triglycidyl ether, reacting at constant temperature for 1h, adding 2, 3-epoxypropyltrimethylammonium chloride, reacting at constant temperature under reflux for 8-9h, evaporating to remove the solvent methanol to obtain a polymer, and washing and drying the polymer by deionized water to obtain the polymer;
adding the polymer prepared in the first step into acetone, adding sodium hydroxyethyl sulfonate into the acetone, heating to 50-60 ℃, stirring and mixing for 3-5min, then dropwise adding toluene diisocyanate into the acetone, stirring and reacting for 6-7h at constant temperature after the dropwise adding is completed, and then filtering and washing to obtain the high imbibition polymer.
2. The preparation process of the new energy lithium ion battery separator according to claim 1, wherein the mass ratio of the polyethylene to the high liquid absorption polymer in the first step is 1: 3.2-3.3, wherein the total mass of the polyethylene and the high liquid absorption polymer added into each kilogram of dimethyl phthalate is 295-302g, and the mass of the polyethylene glycol added into each kilogram of dimethyl phthalate is 134-138 g.
3. The preparation process of the new energy lithium ion battery separator according to claim 1, wherein the molar ratio of melamine to trimethylolpropane triglycidyl ether in step (i) is 1: 0.73-0.76, and the molar ratio of the melamine to the 2, 3-epoxypropyltrimethylammonium chloride is 1: 0.28-0.29.
4. The preparation process of the new energy lithium ion battery separator according to claim 1, wherein 1.49-1.51g of sodium isethionate is added to each gram of polymer in the step (II), and 1.79-1.82g of toluene diisocyanate is added at the same time.
5. The preparation process of the new energy lithium ion battery separator according to claim 1, wherein the preparation process of the imbibing foaming solution is as follows: adding the prepared high liquid absorption polymer into isopropyl acetate, stirring for dissolving, then adding hydroxyl silicone oil, stirring and mixing uniformly, then adding n-pentane and tween 80, adding a sulfuric acid solution with the concentration of 20% after mixing uniformly, and stirring and mixing uniformly at the temperature of 25-30 ℃ to obtain the liquid absorption foaming melt.
6. The preparation process of the new energy lithium ion battery separator as claimed in claim 5, wherein 8-10mL of isopropyl acetate, 0.21-0.23g of hydroxy silicone oil, 0.09-0.1g of Tween 80, 0.09-0.11g of n-pentane and 0.11-0.13g of 20% sulfuric acid solution are added to each gram of high liquid absorption polymer.
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| CN114566757B (en) * | 2021-12-31 | 2023-08-04 | 宁波长阳科技股份有限公司 | Lithium ion battery diaphragm with high strength and high liquid absorption rate and preparation method thereof |
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