CN114899481A - Polyurethane-based polymer solid electrolyte material and preparation method and application thereof - Google Patents
Polyurethane-based polymer solid electrolyte material and preparation method and application thereof Download PDFInfo
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Abstract
A polyurethane-based polymer solid electrolyte material and a preparation method and application thereof belong to the field of lithium ion battery materials, the solid electrolyte material is composed of matrix resin and lithium salt, wherein the matrix resin is obtained by using diisocyanate, polyethylene glycol, a chain extender, a catalyst and an organic solvent as reaction raw materials and adopting a pre-sealing end method for reaction, and the crystallization degree of the polymer solid electrolyte material provided by the invention is reduced by introducing a diisocyanate chain segment, so that the ionic conductivity of the electrolyte is improved; moreover, the hard segment and the soft segment can form a hydrogen bond, and the strong hydrogen bonding effect provides good mechanical property for the polymer electrolyte; the polyurethane has a special soft-hard segment structure, the molecular designability is strong, polyurethane-based polymer solid electrolyte materials with different mechanical properties can be prepared according to application requirements, and meanwhile, the soft segment of the polyurethane can dissolve a large amount of lithium salt and has good flexibility, so that good ion conductivity can be provided.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, relates to a polymer solid electrolyte material, and a preparation method and application thereof, and particularly relates to a polyurethane-based polymer solid electrolyte material, and a preparation method and application thereof.
Background
At present, the all-solid-state lithium ion battery mainly comprises three parts, namely a positive electrode, a solid electrolyte and a negative electrode, and the materials of the all-solid-state lithium ion battery are all solid. Compared with the traditional liquid lithium ion battery, the liquid lithium ion battery has the following advantages: no liquid exists completely, and the damage of electrolyte leakage, corrosion, flammability and explosion is eliminated; liquid does not need to be packaged, the battery assembly and sealing become simple, and the production efficiency and the energy density are improved to a certain degree; a plurality of electrodes can be superposed, and a large-voltage single battery is hopeful to be prepared; the electrochemical window is wide, and can be matched with various high-voltage positive electrode materials, so that the energy density and the power density of the battery are further improved; side reactions are few, and the battery has higher coulombic efficiency and longer cycle life.
Due to the advantages of all-solid-state batteries, the attention of scientific research teams of countries around the world is attracted. Designing and developing a polymer matrix with a novel structure, optimizing the composition of a polymer electrolyte and the structure of an all-solid-state battery are the keys for preparing the high-performance all-solid-state lithium battery.
Chinese patent application publication No. CN106916308A discloses a solid polymer electrolyte for lithium batteries and an all-solid-state lithium battery, wherein the solid polymer is a crosslinked polymer containing polyethylene glycol side chains, and has good cycling stability at room temperature and low temperature, but the polymer electrolyte has low room-temperature ionic conductivity due to the strong crystallinity of polyethylene glycol.
Chinese patent application publication No. CN110474089A discloses a solid polymer electrolyte and an all-solid-state lithium ion battery, where the solid polymer is a crosslinked polymer containing polyethylene glycol, and the all-solid-state lithium ion battery adopts isocyanate crosslinking agent in the electrode material to combine with the solid polymer electrolyte to form a continuous structure of an anode-solid-state polymer electrolyte, so as to eliminate the influence of interface resistance and improve lithium ion migration efficiency, but the solid polymer in the patent has low mechanical properties, and the flexibility of the solid electrolyte cannot meet the requirements of different working environments.
Disclosure of Invention
In view of the above situation, the present invention provides a polyurethane-based polymer solid electrolyte material and a preparation method thereof to overcome the defects of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: the solid electrolyte material is composed of matrix resin and lithium salt, wherein the matrix resin is obtained by reacting diisocyanate, polyethylene glycol, a chain extender, a catalyst and an organic solvent serving as reaction raw materials by a pre-sealing end method;
wherein the mass ratio of the diisocyanate to the polyethylene glycol is 0.1/1-2.4/1, the mass ratio of the diisocyanate to the chain extender is 2/1-4.5/1, the mass ratio of the diisocyanate to the catalyst is 20/1-500/1, and the mass ratio of the matrix resin to the lithium salt is 4/1-20/1.
Preferably, the diisocyanate is an aliphatic diisocyanate or an aromatic diisocyanate; wherein the aliphatic diisocyanate comprises isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and L-lysine diisocyanate, and the aromatic diisocyanate comprises m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
Preferably, the polyethylene glycol has one or more of weight average relative molecular weights of 200, 400, 600, 800, 1000, 1500, 2000, 4000, 8000 and 20000.
Preferably, the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol a, dimethylene phenyl diol, hydroquinone bis-beta-hydroxyethyl.
Preferably, the catalyst is one or more of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, stannous octoate, dibutyltin dilaurate, a triethylene diamine solution with the mass concentration of 33%, a potassium acetate solution, a quaternary ammonium salt, trisphenol, benzyl dimethylamine, dimethylethanolamine, tetramethyl ethylenediamine and tetramethyl propylenediamine.
Preferably, the organic solvent is one or more of acetone, benzene, diethyl ether, N-dimethylacetamide.
Preferably, the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate, lithium perchlorate, lithium chloride and lithium bromide
The preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps:
(1): putting polyethylene glycol into an organic solvent for vacuum dehydration treatment, and carrying out vacuum dehydration treatment on diisocyanate in advance;
(2): cooling the polyethylene glycol organic solution obtained in the step (1) to room temperature to obtain a first dispersion system;
(3): adding an organic diisocyanate solution dissolved with a catalyst into the first dispersion system in the step (2) to obtain a second dispersion system;
(4): stirring the second dispersion system in the step (3), and naturally cooling to room temperature; then adding a chain extender into the second dispersion system to obtain a third dispersion system;
(5): stirring the third dispersion system obtained in the step (4), and cooling to obtain a liquid solution substance;
(6): washing the liquid solution substance, and then drying in vacuum to obtain matrix resin;
(7): and (3) dissolving lithium salt in the matrix resin obtained in the step (6) to prepare slurry, then placing the slurry in a mold, and removing bubbles in a vacuum environment to obtain the polyurethane-based polymer solid electrolyte material.
Preferably, the temperature of the polyethylene glycol vacuum dehydration treatment in the step (1) is 60-120 ℃; the vacuum dewatering treatment temperature of the diisocyanate is 60-90 ℃, and the vacuum dewatering time of the polyethylene glycol and the diisocyanate is 2-24 hours; the mass volume ratio of the polyethylene glycol to the organic solvent is 1g/2.5 mL-1 g/15 mL;
stirring the second dispersion system at 30-90 ℃ for reaction for 2-12 h;
in the step (5), the third dispersion system is stirred and reacted for 2-12 h at the temperature of 30-90 ℃;
washing the liquid solution substance with methanol-acetone in the step (6), and then carrying out vacuum drying for 12-48 h at 50-80 ℃;
the time for removing bubbles in vacuum in the step (7) is 12-36 h.
Compared with the prior art, the invention has the beneficial effects that:
(1): the crystallization degree of the polymer solid electrolyte material provided by the invention is reduced due to the introduction of the diisocyanate chain segment, so that the ionic conductivity of the electrolyte is improved; moreover, the hard segment and the soft segment can form a hydrogen bond, and the strong hydrogen bonding effect provides good mechanical property for the polymer electrolyte; the polyurethane has a special soft-hard segment structure, the molecular designability is strong, polyurethane-based polymer solid electrolyte materials with different mechanical properties can be prepared according to application requirements, and meanwhile, the soft segment of the polyurethane can dissolve a large amount of lithium salt and has good flexibility, so that good ion conductivity can be provided;
(2): the polymer solid electrolyte material provided by the invention has excellent heat resistance, so that the safety of the lithium ion battery working in a high-temperature environment is ensured;
(3): the preparation process of the solid electrolyte material mainly adopts industrial raw materials, so that the production cost is reduced, the preparation method is quick, efficient and strong in controllability, and meanwhile, the production of the electrolyte by using a clean and efficient technology meets the requirement of environmental protection, so that large-scale industrial production becomes possible.
Drawings
FIG. 1: a photograph of a real object of the polyurethane-based polymer solid electrolyte material prepared by the method of example 1 of the present invention was shown to be a transparent flexible film.
FIG. 2 is a schematic diagram: is the ionic conductivity of the polyurethane-based polymer solid electrolyte material prepared by the method described in example 1 of the present invention.
FIG. 3: is the thermal weight loss performance of the polyurethane-based polymer solid electrolyte material prepared by the method described in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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 invention provides a polyurethane-based polymer solid electrolyte material which is composed of matrix resin and lithium salt, wherein the matrix resin is obtained by reacting diisocyanate, polyethylene glycol, a chain extender, a catalyst and an organic solvent serving as reaction raw materials by a pre-sealing end method. The catalyst and the chain extender have the effects of enabling raw materials to be more fully reflected, improving the film forming property of the raw materials, enabling the production efficiency to be better and saving the consumed raw materials and energy.
The mass ratio of the diisocyanate to the polyethylene glycol is 0.1/1-2.4/1, the mass ratio of the diisocyanate to the chain extender is 2/1-4.5/1, the mass ratio of the diisocyanate to the catalyst is 20/1-500/1, and the mass ratio of the matrix resin to the lithium salt is 4/1-20/1.
The diisocyanate is aliphatic diisocyanate or aromatic diisocyanate; wherein the aliphatic diisocyanate comprises isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and L-lysine diisocyanate, and the aromatic diisocyanate comprises m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
Wherein, the molecular weight of the polyethylene glycol structural formula is changed along with the change of n value in the structural formula as shown in the following structure.
Wherein, the structural formula of the aliphatic diisocyanate is as follows.
The structural formula of the aromatic diisocyanate is as follows.
The polyethylene glycol has a weight average relative molecular weight of 200, 400, 600, 800, 1000, 1500, 2000, 4000, 8000, 20000.
The chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, dimethylene phenyl glycol and hydroquinone bis-beta-hydroxyethyl.
The catalyst is one or more of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, stannous octoate, dibutyltin dilaurate, a triethylene diamine solution with the mass concentration of 33%, a potassium acetate solution, a quaternary ammonium salt, trisphenol, benzyl dimethylamine, dimethyl ethanolamine, tetramethyl ethylenediamine and tetramethyl propylenediamine.
The organic solvent is one or more of acetone, benzene, diethyl ether and N, N-dimethylacetamide.
The lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium trifluoromethanesulfonate, lithium perchlorate, lithium chloride and lithium bromide
The preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps:
(1): placing polyethylene glycol in an organic solvent, carrying out vacuum dehydration treatment for 2-24 h at 60-120 ℃, and carrying out vacuum dehydration treatment on diisocyanate for 2-24 h at 60-90 ℃; wherein the mass-volume ratio of the polyethylene glycol to the organic solvent is 1g/2.5 mL-1 g/15 mL;
(2): cooling the polyethylene glycol organic solution obtained in the step (1) to room temperature to obtain a first dispersion system;
(3): adding a diisocyanate organic solution dissolved with a catalyst into the first dispersion system obtained in the step (2) to obtain a second dispersion system; then, stirring the second dispersion system at 30-90 ℃ for reaction for 2-12 h, and naturally cooling to room temperature;
(4): adding a chain extender into the second dispersion system obtained in the step (3) to obtain a third dispersion system; then, stirring the third dispersion system at 30-90 ℃ for reaction for 2-12 h, and cooling to obtain a liquid solution substance;
(5): washing the liquid solution substance obtained in the step (3) with methanol-acetone, and then drying in vacuum at 50-80 ℃ for 12-48 h to obtain matrix resin of the polyurethane-based polymer solid electrolyte;
(6): dissolving lithium salt in the matrix resin obtained in the step (5) to prepare slurry;
(7): and (3) placing the slurry obtained in the step (6) in a mold, and removing bubbles in a vacuum environment at 60-70 ℃ to obtain the polyurethane-based polymer solid electrolyte material of the all-solid-state lithium battery, wherein the time for removing bubbles in vacuum is 12-36 h.
The reaction solvent involved in the preparation method needs high-temperature vacuum dehydration, the reaction process needs to be anhydrous and anaerobic to isolate the external environment, the temperature is accurately controlled, and the reaction reagent is added dropwise and slowly, so that the mild and orderly reaction process can be ensured, and the required polyurethane-based polymer solid electrolyte materials of different types can be obtained.
The polyurethane-based polymer solid electrolyte material is particularly suitable for lithium ion batteries, and is a solid electrolyte material for lithium ion batteries.
Example 1: the preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: weighing 1.0g of polyethylene glycol (molecular weight 200), adding 5mL of N, N-dimethylacetamide, placing in an oil bath pot isolated from air, heating to 120 ℃, vacuumizing for 4h to extract water, and naturally cooling to room temperature. 2.4g of p-Phenylene Diisocyanate (PDI) which is dried in vacuum at 60 ℃ and is dewatered is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolution, and the mixture is vibrated for 30min by ultrasonic 80% power. Slowly and dropwise adding a p-Phenylene Diisocyanate (PDI) solution into a polyethylene glycol solution cooled to room temperature, measuring 4mL of N, N-dimethylacetamide, washing in a p-Phenylene Diisocyanate (PDI) solvent bottle, dropwise adding a washing solution into the p-Phenylene Diisocyanate (PDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.9g of chain extender, dissolving the chain extender in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into a p-Phenylene Diisocyanate (PDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the p-Phenylene Diisocyanate (PDI) -polyethylene glycol-chain extender, heating the solution to 75 ℃ for reaction for about 4 hours, naturally cooling the solution to room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 2:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: weighing 1.0g of polyethylene glycol (molecular weight is 400), adding 5mL of N, N-dimethylacetamide, placing in an oil bath pot isolated from air, heating, vacuumizing for 4h when the temperature reaches 120 ℃, pumping out water, and naturally cooling to room temperature. Weighing 1.2g of m-Phenylene Diisocyanate (PDI) which is dried in vacuum at 60 ℃ and is dewatered, adding 0.01g of catalyst, immediately adding 4mL of N, N-dimethylacetamide to dissolve, and oscillating for 30min with ultrasonic 80% power. Slowly dropwise adding an m-Phenylene Diisocyanate (PDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into an m-Phenylene Diisocyanate (PDI) solvent bottle, washing, dropwise adding a washing solution into the m-Phenylene Diisocyanate (PDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.5g of chain extender, dissolving in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into a solution of m-Phenylene Diisocyanate (PDI) -polyethylene glycol, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the solution of m-Phenylene Diisocyanate (PDI) -polyethylene glycol-chain extender, heating, reacting at 75 ℃ for about 4 hours, naturally cooling to room temperature to obtain a liquid polymer, and washing with methanol-acetone to obtain the relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the lithium salt into 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product into a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 3:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: weighing 1.0g of polyethylene glycol (molecular weight is 600), adding 5mL of N, N-dimethylacetamide, placing in an oil bath pot isolated from air, heating, vacuumizing for 4h when the temperature reaches 120 ℃, then pumping out water, naturally cooling to room temperature, weighing 0.8g of Hexamethylene Diisocyanate (HDI) which is dried and dewatered in vacuum at 60 ℃, adding 0.01g of catalyst, immediately adding 4mL of N, N-dimethylacetamide, dissolving, and oscillating with ultrasonic 80% power for 30 min. Slowly and dropwise adding a Hexamethylene Diisocyanate (HDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a Hexamethylene Diisocyanate (HDI) solvent bottle for cleaning, dropwise adding a cleaning solution into Hexamethylene Diisocyanate (HDI) -polyethylene glycol, then, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.3g of chain extender 1, 4-butanediol, dissolving in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into a Hexamethylene Diisocyanate (HDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the Hexamethylene Diisocyanate (HDI) -polyethylene glycol-chain extender, heating the solution to 75 ℃ for reaction for about 4 hours, naturally cooling the solution to room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain a relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 4:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: weighing 1.0g of polyethylene glycol (molecular weight is 800), adding 5mL of N, N-dimethylacetamide, placing in an oil bath pot isolated from air, heating, vacuumizing for 4h when the temperature reaches 120 ℃, pumping out water, and naturally cooling to room temperature. 0.7g of 2, 4-Toluene Diisocyanate (TDI) dried in vacuum at 60 ℃ to remove water is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolution, and the mixture is subjected to ultrasonic oscillation with the power of 80% for 30 min. Slowly and dropwise adding a 2, 4-Toluene Diisocyanate (TDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a 2, 4-Toluene Diisocyanate (TDI) solvent bottle, washing, dropwise adding a washing solution into 2, 4-Toluene Diisocyanate (TDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.2g of chain extender, dissolving the chain extender in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into 2, 4-Toluene Diisocyanate (TDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the 2, 4-Toluene Diisocyanate (TDI) -polyethylene glycol-chain extender, heating the solution to 75 ℃ for reacting for about 4 hours, naturally cooling the solution to room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain the pure matrix resin.
And (3) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, placing the dissolved product in a film to prepare a film, and preparing the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 5:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (molecular weight is 1000) is weighed, 5mL of N, N-dimethylacetamide is added into an oil bath pan isolated from air, the temperature is raised, when the temperature reaches 120 ℃, vacuum pumping is carried out for 4 hours, moisture in the oil is pumped out, and then the oil is naturally cooled to room temperature. Weighing 1.0g of 2, 6-Toluene Diisocyanate (TDI) which is dried in vacuum at 60 ℃ and is dehydrated, adding 0.01g of catalyst, immediately adding 4mL of N, N-dimethylacetamide to dissolve, and oscillating for 30min with ultrasonic 80% power. Slowly and dropwise adding a 2, 6-Toluene Diisocyanate (TDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a 2, 6-Toluene Diisocyanate (TDI) solvent bottle, washing, dropwise adding a washing solution into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.4g of chain extender, dissolving in 1mL of N, N-dimethylacetamide, slowly dropwise adding into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol-chain extender, heating, reacting at 75 ℃ for about 4 hours, naturally cooling to room temperature to obtain a liquid polymer, and washing with methanol-acetone to obtain the relatively pure matrix resin.
And (3) putting the prepared matrix resin into a vacuum drying oven, drying for 24h at 60 ℃, taking 0.1g of the dried polymer electrolyte, adding 0.02g of lithium salt, dissolving in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, putting the dissolved product into a film, and preparing the film to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 6:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (with the molecular weight of 1500) is weighed, 5mL of N, N-dimethylacetamide is added into an oil bath pan isolated from air, the oil bath pan is heated, when the temperature reaches 120 ℃, the oil bath pan is vacuumized for 4 hours, water in the oil bath pan is pumped out, and then the oil bath pan is naturally cooled to room temperature. 0.9g of 2, 6-Toluene Diisocyanate (TDI) dried in vacuum at 60 ℃ to remove water is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolution, and the mixture is subjected to ultrasonic oscillation with the power of 80% for 30 min. Slowly and dropwise adding a 2, 6-Toluene Diisocyanate (TDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a 2, 6-Toluene Diisocyanate (TDI) solvent bottle, washing, dropwise adding a washing solution into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.2g of chain extender, dissolving in 1mL of N, N-dimethylacetamide, slowly and dropwise adding into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into 2, 6-Toluene Diisocyanate (TDI) -polyethylene glycol-chain extender, heating, reacting at 75 ℃ for about 4 hours, naturally cooling to room temperature to obtain a liquid polymer, and washing with methanol-acetone to obtain the relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 7:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (molecular weight 2000) is weighed, 5mL of N, N-dimethylacetamide is added into the mixture, the mixture is placed in an oil bath pot without air, the temperature is raised until the temperature reaches 120 ℃, the mixture is vacuumized for 4 hours, water in the mixture is pumped out, and then the mixture is naturally cooled to room temperature. Weighing 0.7g of L-Lysine Diisocyanate (LDI) which is dried in vacuum at 60 ℃ and is dewatered, adding 0.01g of catalyst, immediately adding 4mL of N, N-dimethylacetamide to dissolve, and oscillating for 30min with ultrasonic 80% power. Slowly and dropwise adding an L-Lysine Diisocyanate (LDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into an L-Lysine Diisocyanate (LDI) solvent bottle, washing, dropwise adding a washing solution into L-Lysine Diisocyanate (LDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.2g of chain extender, dissolving in 1mL of N, N-dimethylacetamide, slowly dropwise adding into an L-Lysine Diisocyanate (LDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the L-Lysine Diisocyanate (LDI) -polyethylene glycol-chain extender, heating, reacting at 75 ℃ for about 4 hours, naturally cooling to room temperature to obtain a liquid polymer, and washing with methanol-acetone to obtain a relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 8:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (with the molecular weight of 4000) is weighed, 5mL of N, N-dimethylacetamide is added into an oil bath pan isolated from air, the oil bath pan is heated, when the temperature reaches 120 ℃, the oil bath pan is vacuumized for 4 hours, water in the oil bath pan is pumped out, and then the oil bath pan is naturally cooled to the room temperature. 0.4g of diphenylmethane diisocyanate (MDI) which is dried in vacuum at 60 ℃ to remove water is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolution, and the mixture is vibrated for 30min by ultrasonic 80% power. Slowly and dropwise adding a diphenylmethane diisocyanate (MDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a diphenylmethane diisocyanate (MDI) solvent bottle, washing, dropwise adding the washing solution into the diphenylmethane diisocyanate (MDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.1g of chain extender, dissolving the chain extender in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into diphenylmethane diisocyanate (MDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the diphenylmethane diisocyanate (MDI) -polyethylene glycol-chain extender, heating the mixture to the temperature of 75 ℃ for reaction for about 4 hours, naturally cooling the mixture to the room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 9:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (molecular weight of 8000) is weighed, 5mL of N, N-dimethylacetamide is added into an oil bath pan isolated from air, the temperature is raised, when the temperature reaches 120 ℃, vacuum pumping is carried out for 4 hours, moisture in the oil is pumped out, and then the oil is naturally cooled to room temperature. 0.2g of diphenylmethane diisocyanate (MDI) which is dried in vacuum at 60 ℃ to remove water is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolving, and the mixture is vibrated for 30min by ultrasonic 80% power. Slowly and dropwise adding a diphenylmethane diisocyanate (MDI) solution into a polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a diphenylmethane diisocyanate (MDI) solvent bottle, washing, dropwise adding the washing solution into the diphenylmethane diisocyanate (MDI) -polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.1g of chain extender, dissolving the chain extender in 1mL of N, N-dimethylacetamide, slowly dropwise adding the chain extender into diphenylmethane diisocyanate (MDI) -polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the diphenylmethane diisocyanate (MDI) -polyethylene glycol-chain extender, heating the mixture to the temperature of 75 ℃ for reaction for about 4 hours, naturally cooling the mixture to the room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, taking 0.1g of the dried polymer electrolyte, adding 0.02g of lithium salt, dissolving in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, placing the dissolved product in a film to prepare a film, and preparing the lithium salt-added polyurethane-based polymer solid electrolyte.
Example 10:
the concrete preparation method of the polyurethane-based polymer solid electrolyte material comprises the following steps: 2.0g of polyethylene glycol (molecular weight 2000) is weighed, 5mL of N, N-dimethylacetamide is added into the mixture, the mixture is placed in an oil bath pot without air, the temperature is raised until the temperature reaches 120 ℃, the mixture is vacuumized for 4 hours, water in the mixture is pumped out, and then the mixture is naturally cooled to room temperature. 0.5g of Hexamethylene Diisocyanate (HDI) which is dried in vacuum at 60 ℃ to remove water is weighed, 0.01g of catalyst is added, 4mL of N, N-dimethylacetamide is added immediately for dissolution, and the mixture is shaken for 30min with ultrasonic 80% power. Slowly and dropwise adding the hexamethylene diisocyanate solution into the polyethylene glycol solution cooled to room temperature, adding 4mL of N, N-dimethylacetamide into a hexamethylene diisocyanate solvent bottle, washing, dropwise adding the washing solution into the hexamethylene diisocyanate-polyethylene glycol, heating to 70 ℃, reacting for about 4 hours, and naturally cooling to room temperature. Weighing 0.2g of chain extender, dissolving the chain extender in 1mL of N, N-dimethylacetamide, slowly and dropwise adding the chain extender into a hexamethylene diisocyanate-polyethylene glycol solution, adding 1mL of N, N-dimethylacetamide to clean the chain extender, dropwise adding the cleaning solution into the hexamethylene diisocyanate-polyethylene glycol-chain extender, heating the mixture to react for about 4 hours at the temperature of 75 ℃, naturally cooling the mixture to room temperature to obtain a liquid polymer, and washing the liquid polymer with methanol-acetone to obtain relatively pure matrix resin.
And (2) drying the prepared matrix resin in a vacuum drying oven at 60 ℃ for 24h, adding 0.02g of lithium salt into 0.1g of the dried matrix resin, dissolving the mixture in 2mL of N, N-dimethylacetamide, adding a rotor, rotating for 12h, and placing the dissolved product in a film to prepare a film so as to obtain the lithium salt-added polyurethane-based polymer solid electrolyte.
The test method comprises the following steps:
the tensile strength of the polyurethane-based polymer solid electrolyte materials prepared in examples 1 to 10 (tensile strength was measured using a polymer tensile strength tester) was as shown in table 1.
The ionic conductivity test results of the polyurethane-based polymer solid electrolyte materials prepared in examples 1 to 10 are shown in table 1.
Table 1 test of properties of polyurethane-based polymer solid electrolyte materials prepared in examples 1 to 10.
| Item | Room temperature ionic conductivity/S cm -1 | Tensile strength/MPa |
| Example 1 | 3.91×10 -4 | 16.2 |
| Example 2 | 8.39×10 -5 | 15.7 |
| Example 3 | 7.63×10 -5 | 15.9 |
| Example 4 | 7.26×10 -5 | 12.6 |
| Example 5 | 1.32×10 -4 | 13.1 |
| Example 6 | 2.68×10 -4 | 14.5 |
| Example 7 | 3.77×10 -4 | 15.2 |
| Example 8 | 9.69×10 -5 | 14.9 |
| Example 9 | 9.57×10 -5 | 16.7 |
| Example 10 | 3.26×10 -4 | 12.3 |
As can be seen from the examples in Table 1, the tensile strength of the polyurethane-based polymer solid electrolyte materials prepared in examples 1 to 10 is higher than 12MPa, which indicates that the polyurethane-based polymer solid electrolyte generally has higher mechanical strength, and the performance has an important influence on improving the safety performance of the battery. And the room-temperature ionic conductivity meets the requirement of solid-state battery circulation, and the comprehensive comparative example 1 has the best comprehensive performance and has great advantages in the aspects of tensile strength and ionic conductivity.
As a result of comparing the ionic conductivity of the polyurethane-based polymer solid electrolyte prepared in example 1 with that of a conventional polymer solid electrolyte in the prior art, as shown in fig. 2, the polyurethane-based polymer solid electrolyte prepared in example 1 has better ionic conductivity.
The results of the thermogravimetric performance test of the polyurethane-based polymer solid electrolyte prepared in example 1 compared with the ionic conductivity of the conventional polymer solid electrolyte in the prior art are shown in fig. 3, and the test shows that the polyurethane-based polymer solid electrolyte prepared in example 1 can resist heat up to 300 ℃ and does not decompose, thereby providing good application prospects for the preparation of lithium ion batteries.
The polyurethane-based polymer solid electrolyte material prepared in example 1 was assembled into an all-solid battery: lithium iron phosphate is used as a positive electrode, metal lithium is used as a negative electrode, and the polyurethane-based solid polymer electrolyte is arranged between the positive electrode and the negative electrode without adding electrolyte. The initial charge-discharge capacity of the obtained all-solid-state battery reaches 155mAh/g, and after 100 cycles, the discharge capacity is reduced to 139mAh/g, and the capacity of nearly 89.7 percent is maintained.
In summary, the polyurethane-based polymer solid electrolyte material has good ionic conductivity, heat resistance and mechanical properties, so that it is one of the preferred materials for all-solid-state lithium ions.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention by equivalent replacement or change according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (10)
1. The polyurethane-based polymer solid electrolyte material is characterized by comprising matrix resin and lithium salt, wherein the matrix resin is obtained by reacting diisocyanate, polyethylene glycol, a chain extender, a catalyst and an organic solvent serving as reaction raw materials by a pre-sealing end method;
the mass ratio of the diisocyanate to the polyethylene glycol is 0.1/1-2.4/1, the mass ratio of the diisocyanate to the chain extender is 2/1-4.5/1, the mass ratio of the diisocyanate to the catalyst is 20/1-500/1, and the mass ratio of the matrix resin to the lithium salt is 4/1-20/1.
2. The polyurethane-based polymer solid electrolyte material according to claim 1, characterized in that the diisocyanate is an aliphatic diisocyanate or an aromatic diisocyanate; wherein the aliphatic diisocyanate comprises isophorone diisocyanate, hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate and L-lysine diisocyanate, and the aromatic diisocyanate comprises m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
3. The polyurethane-based polymer solid electrolyte material according to claim 1, wherein the polyethylene glycol employs one or more of weight average relative molecular weights of 200, 400, 600, 800, 1000, 1500, 2000, 4000, 8000, 20000.
4. The polyurethane-based polymer solid electrolyte material according to claim 1, wherein the chain extender is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol a, dimethylene phenyl diol, hydroquinone bis- β -hydroxyethyl.
5. The polyurethane-based polymer solid electrolyte material according to claim 1, wherein the catalyst is one or more of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, stannous octoate, dibutyltin dilaurate, a 33% by mass solution of triethylene diamine, a potassium acetate solution, a quaternary ammonium salt, trisphenol, benzyl dimethylamine, dimethylethanolamine, tetramethylethylenediamine, and tetramethylpropylenediamine.
6. The polyurethane-based polymer solid electrolyte material according to claim 1, wherein the organic solvent is one or more of acetone, benzene, diethyl ether, N-dimethylacetamide.
7. The polyurethane-based polymer solid electrolyte material according to claim 1, wherein the lithium salt is one or more of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethylsulfonyl imide, lithium bisfluorosulfonyl imide, lithium trifluoromethanesulfonate, lithium perchlorate, lithium chloride, and lithium bromide.
8. The method for producing a polyurethane-based polymer solid electrolyte material according to claim 1, comprising the steps of:
(1): putting polyethylene glycol into an organic solvent for vacuum dehydration treatment, and carrying out vacuum dehydration treatment on diisocyanate in advance;
(2): cooling the polyethylene glycol organic solution obtained in the step (1) to room temperature to obtain a first dispersion system;
(3): adding an organic diisocyanate solution dissolved with a catalyst into the first dispersion system in the step (2) to obtain a second dispersion system;
(4): stirring the second dispersion system in the step (3), and naturally cooling to room temperature; then adding a chain extender into the second dispersion system to obtain a third dispersion system;
(5): stirring the third dispersion system obtained in the step (4), and cooling to obtain a liquid solution substance;
(6): washing the liquid solution substance, and then drying in vacuum to obtain matrix resin;
(7): and (3) dissolving lithium salt in the matrix resin obtained in the step (6) to prepare slurry, then placing the slurry in a mold, and removing bubbles in a vacuum environment to obtain the polyurethane-based polymer solid electrolyte material.
9. The method for preparing the polyurethane-based polymer solid electrolyte material according to claim 8, wherein the temperature of the vacuum dehydration treatment of polyethylene glycol in the step (1) is 60-120 ℃; the vacuum dewatering treatment temperature of the diisocyanate is 60-90 ℃, and the vacuum dewatering time of the polyethylene glycol and the diisocyanate is 2-24 hours; the mass volume ratio of the polyethylene glycol to the organic solvent is 1g/2.5 mL-1 g/15 mL;
stirring the second dispersion system at 30-90 ℃ for reaction for 2-12 h;
in the step (5), the third dispersion system is stirred and reacted for 2-12 h at the temperature of 30-90 ℃;
washing the liquid solution substance with methanol-acetone in the step (6), and then carrying out vacuum drying for 12-48 h at the temperature of 50-80 ℃;
the time for removing bubbles in vacuum in the step (7) is 12-36 h.
10. The use of the polyurethane-based polymer solid electrolyte material of any one of claims 1 to 7 in the field of lithium ion batteries.
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| CN117551244A (en) * | 2023-02-16 | 2024-02-13 | 吉林省翰驰科技有限公司 | Block polymer, preparation method and application thereof, solid electrolyte and application thereof |
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| CN115572364A (en) * | 2022-11-07 | 2023-01-06 | 重庆宏国聚材科技有限责任公司 | Solvent type high-molecular phosphate and preparation method and application thereof |
| CN117551244A (en) * | 2023-02-16 | 2024-02-13 | 吉林省翰驰科技有限公司 | Block polymer, preparation method and application thereof, solid electrolyte and application thereof |
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