CN116014227A - Composite material and preparation method thereof, composite gel electrolyte and preparation method and application thereof - Google Patents
Composite material and preparation method thereof, composite gel electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium batteries, in particular to a composite material and a preparation method thereof, a composite gel electrolyte and a preparation method and application thereof. The composite material comprises inorganic nano particles and polymers coated on the surfaces of the inorganic nano particles through in-situ polymerization; inorganic nanoparticles include POSS and derivatives thereof and/or halloysite; the polymerized monomers include a first polymerized monomer, a second polymerized monomer, and a third polymerized monomer; the first polymerization monomer comprises unsaturated olefin compound containing epoxy group; the second polymeric monomer comprises acrylonitrile or a derivative of acrylonitrile; the third polymeric monomer comprises a multi-arm polyethylene glycol maleimide and/or a multi-arm polyethylene glycol acrylate. The inorganic nano particles can increase incombustible components in the system and improve the intrinsic safety of the material; the polymer can ensure the conduction of lithium ions; the polymer is coated on the surface of the inorganic nano particles through in-situ polymerization, so that the problem of interfacial pain points in the solid-state battery is solved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a composite material and a preparation method thereof, a composite gel electrolyte and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the fields of 3C, power batteries, energy storage and the like due to the advantages of high energy density, high output power, long cycle life and the like. The electrolyte of the traditional lithium ion battery is a liquid system, and the battery still has risks of leakage, ignition, combustion, explosion and the like in the long-term use process of the battery. Meanwhile, since a high energy density lithium ion battery generally uses a ternary system of 622 or 822, mn 2+ Dissolution is inevitable in the whole battery system. The continuous dissolution, diffusion and deposition processes of the transition metal cause continuous damage to the SEI film on the negative electrode side of the battery, resulting in degradation of the cycling stability of the battery.
In order to solve the safety problem of lithium ion batteries, researchers often add some flame retardant components, such as triethyl phosphate, fluoroethylene carbonate, and propylene trifluorocarbonate, to the existing electrolyte systems. But still be liquid in terms of the electrolyte itself. With electrolytes that add these components, the battery is still subject to leakage, corrosion of components, and the possibility of battery failure.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a composite material to solve the technical problems of liquid electrolyte leakage and the like possibly caused by liquid electrolyte in the prior art.
In order to achieve the above object of the present invention, the following technical solutions are adopted:
the composite material comprises inorganic nano particles and polymers coated on the surfaces of the inorganic nano particles through in-situ polymerization;
the inorganic nanoparticles comprise at least one of POSS and derivatives thereof and halloysite;
the polymerized monomers of the polymer include a first polymerized monomer, a second polymerized monomer, and a third polymerized monomer;
the first polymerization monomer comprises unsaturated olefin compounds containing epoxy groups;
the second polymeric monomer comprises acrylonitrile or a derivative of acrylonitrile;
the third polymeric monomer comprises multi-arm polyethylene glycol maleimide and/or multi-arm polyethylene glycol acrylate.
According to the composite material, the corresponding polymer is polymerized and coated on the surface of the inorganic nano particles in situ, and the inorganic nano particles can increase incombustible components in a system and improve the intrinsic safety of the material; the polymer can ensure the conduction of lithium ions. And the polymer is coated on the surface of the inorganic nano particles through in-situ polymerization, so that the problem of interfacial pain points in the solid-state battery is solved.
In a specific embodiment of the present invention, in the polymerized monomers of the polymer, the molar ratio of the first polymerized monomer to the second polymerized monomer is (0.7 to 2): 1, a step of; the mass ratio of the first polymerized monomer to the third polymerized monomer is (2.5-400): 1.
in a specific embodiment of the present invention, the mass of the inorganic nanoparticles is 0.01% to 20.0% of the total mass of the polymerized monomers.
Another object of the present invention is to provide a method for preparing a composite material, comprising the steps of:
the first polymerization monomer, the second polymerization monomer, the third polymerization monomer and the inorganic nano particles are subjected to in-situ polymerization reaction in a solvent under the action of an initiator;
and drying the material subjected to the in-situ polymerization reaction.
In a specific embodiment of the present invention, the drying treatment method includes: any one or more of freeze drying, air drying and vacuum drying.
In a specific embodiment of the invention, the temperature of the in situ polymerization reaction is 30-70 ℃; the time of the in-situ polymerization reaction is 20-40 h.
In a specific embodiment of the invention, a gradient heating mode is adopted in the in-situ polymerization reaction. Further, the gradient heating includes: the temperature is kept at 30-33 ℃ for 1-2 h, 40-43 ℃ for 1-2 h, 50-53 ℃ for 1-2 h and 55-70 ℃ for 17-24 h.
It is a further object of the present invention to provide a composite gel electrolyte comprising an electrolyte solution and any of the above described composite materials.
The composite gel electrolyte provided by the invention has a certain self-supporting effect after gelation treatment, and can anchor the liquid component in the main body, so that the risk of liquid leakage is greatly reduced, and the safety performance is improved. And the composite gel electrolyte provided by the invention has a higher limiting oxygen index.
In a specific embodiment of the invention, in the composite gel electrolyte, the mass fraction of the composite material is 0.8% -5.0%.
The invention also provides a preparation method of any one of the composite gel electrolyte, which comprises the following steps:
the composite material is dissolved in an electrolyte solution and subjected to gelation treatment.
In a specific embodiment of the present invention, the gelation treatment includes: heating at 45-50 deg.c.
The invention also provides a lithium ion battery, which comprises any one of the composite gel electrolyte.
The lithium ion battery has excellent cycle performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the composite material, the inorganic nano particles can increase incombustible components in the system, so that the intrinsic safety of the material is improved; the polymer can ensure the conduction of lithium ions; and in-situ polymerization of the coated polymer and the inorganic nano particles solves the problem of interfacial pain points in the solid-state battery.
(2) The composite gel electrolyte disclosed by the invention can anchor the liquid component in the main body, so that the risk of liquid leakage is greatly reduced, and the safety performance is improved; meanwhile, the composite gel electrolyte provided by the invention has higher limiting oxygen index, higher lithium ion conductivity and stable electrochemical window.
(3) The composite gel electrolyte can be directly used in the existing lithium ion battery, and has the advantages of high efficiency, safety and convenience; the prepared lithium ion battery has excellent cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a composite material according to some embodiments of the present invention;
fig. 2 is an optical photograph of the composite gel electrolyte provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The composite material comprises inorganic nano particles and polymers coated on the surfaces of the inorganic nano particles through in-situ polymerization;
the inorganic nanoparticles comprise at least one of POSS and derivatives thereof and halloysite;
the polymerized monomers of the polymer include a first polymerized monomer, a second polymerized monomer, and a third polymerized monomer;
the first polymerization monomer comprises unsaturated olefin compounds containing epoxy groups;
the second polymeric monomer comprises acrylonitrile or a derivative of acrylonitrile;
the third polymeric monomer comprises multi-arm polyethylene glycol maleimide and/or multi-arm polyethylene glycol acrylate.
According to the composite material, the corresponding polymer is polymerized and coated on the surface of the inorganic nano particles in situ, and the inorganic nano particles can increase incombustible components in a system and improve the intrinsic safety of the material; the polymer can ensure the conduction of lithium ions. And the polymer is coated on the surface of the inorganic nano particles through in-situ polymerization, so that the problem of interfacial pain points in the solid-state battery is solved.
A schematic structural diagram of the composite material of the present invention is shown in fig. 1; in the composite material, the organic chain segment of the polymer is polymerized and coated on the surface of the inorganic nano particle in situ to form inorganic particles M, and the inorganic particles M are taken as cores to grow in situ in a polymerized manner, so that a three-dimensional polymer network structure formed by the organic chain segment is formed between adjacent inorganic particles M. On the other hand, the composite material of the invention mainly comprises polymer and inorganic particles M coated with the polymer; for the sake of illustration, there may be inorganic nanoparticles, such as inorganic particles B, which are not partially coated with a polymer, the content of which is not limited.
In particular embodiments of the present invention, the POSS and its derivatives include POSS (polyhedral oligomeric silsesquioxanes), hydroxyl POSS, amino POSS, and the like.
In a specific embodiment of the present invention, the first polymeric monomer comprises any one or more of glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and 2, 3-epoxypropyl acrylate octadecenoic acid.
In a specific embodiment of the present invention, the second polymeric monomer comprises any one or more of 3-cyclopentylacrylonitrile, 3-phenylacrylonitrile, acrylonitrile, 3- (benzenesulfonyl) acrylonitrile, and 3-ethoxyacrylonitrile.
In a specific embodiment of the present invention, the third polymeric monomer comprises a four-arm polyethylene glycol maleimide and/or a four-arm polyethylene glycol acrylate.
In a specific embodiment of the invention, the weight average molecular weight of the four-arm polyethylene glycol maleimide is 2000-20000 Da, such as 5000Da; the weight average molecular weight of the four-arm polyethylene glycol acrylate is 1000-20000 Da, such as 2000Da.
As in the various embodiments, the weight average molecular weight of the four-arm polyethylene glycol maleimide may be exemplified by 2000Da, 4000Da, 5000Da, 8000Da, 10000Da, 12000Da, 15000Da, 18000Da, 20000Da, etc.; the weight average molecular weight of the four-arm polyethylene glycol acrylate may be exemplified by 1000Da, 2000Da, 5000Da, 8000Da, 10000Da, 12000Da, 15000Da, 18000Da, 20000Da, etc.
In a specific embodiment of the present invention, the molar ratio of the first polymerized monomer to the second polymerized monomer in the polymerized monomers of the polymer is (0.7 to 2):1, such as (1.3 to 1.4): 1, a step of; the mass ratio of the first polymerized monomer to the third polymerized monomer is (2.5-400): 1, such as (35-45): 1.
as in the various embodiments, the molar ratio of the first and second polymeric monomers in the polymeric monomer may be exemplified by 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc.; the mass ratio of the first polymerized monomer to the third polymerized monomer may be exemplified by 2.5: 1. 5.0: 1. 10.0: 1. 15.0: 1. 20:1. 40: 1. 60: 1. 100: 1. 200: 1. 400:1, etc.
In a specific embodiment of the present invention, the mass of the inorganic nanoparticles is 0.01% to 20.0%, such as 0.5% to 5.5%, of the total mass of the polymerized monomers.
As in the various embodiments, the mass of the inorganic nanoparticles may be exemplified by 0.01%, 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, etc. of the total mass of the polymerized monomers.
The limit oxygen index, the safety performance, the cycle performance and the like of the composite gel electrolyte obtained from the composite material are further ensured by adopting the proper dosage of the inorganic nano particles.
Another object of the present invention is to provide a method for preparing a composite material, comprising the steps of:
the first polymerization monomer, the second polymerization monomer, the third polymerization monomer and the inorganic nano particles are subjected to in-situ polymerization reaction in a solvent under the action of an initiator;
and drying the material subjected to the in-situ polymerization reaction.
In a specific embodiment of the present invention, the drying treatment method includes: any one or more of freeze drying, air drying and vacuum drying.
In a specific embodiment of the present invention, the freeze-drying comprises: and (3) pre-freezing the materials, and then performing vacuum freeze drying treatment. Wherein, the pre-freezing time can be 3-5 hours, such as 4 hours; the time of the vacuum freeze-drying treatment may be 16 to 20 hours, such as 18 hours.
In a specific embodiment of the present invention, the temperature of the air-drying is 60 to 90 ℃, and the time of the air-drying is 4 to 10 hours.
In a specific embodiment of the present invention, the temperature of the vacuum drying is 60 to 90 ℃, and the time of the vacuum drying is 4 to 48 hours.
The specific time of freeze drying, forced air drying and vacuum drying treatment can be adjusted according to the actual drying condition, and the drying treatment mode is adopted to remove the solvent and incompletely reacted monomers in the materials, so that the purity of the composite material is improved.
In a specific embodiment of the present invention, the solvent comprises a non-aqueous organic solvent. Further, the solvent includes any one or more of dimethyl carbonate, methylethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1, 3-dioxolane, ethyl acetate, gamma-butyrolactone, 6-caprolactone, acetonitrile and sulfolane.
The solvent is a solvent commonly used in lithium ion battery electrolyte, on one hand, the solvent can ensure that each component performs in-situ polymerization reaction in a corresponding solution system; on the other hand, after the drying treatment, even if a trace amount of solvent residues possibly exist, the stable operation of the battery can be ensured, and other impurities can not be introduced.
In a specific embodiment of the present invention, the solvent comprises dimethyl carbonate and ethyl methyl carbonate. Further, in the solvent, the volume ratio of dimethyl carbonate to ethylmethyl carbonate is 1:1.
In a specific embodiment of the present invention, the ratio of the amount of the solvent to the sum of the masses of the first, second and third polymeric monomers is (2.9904 to 5.607) mL/1 g. It is meant herein that the amount of solvent used is (2.990 to 5.607) mL per 1g of the mixture of the three polymerized monomers, and is not limited to the specific amounts of polymerized monomers and solvent used.
In various embodiments, the ratio of the amount of solvent to the sum of the masses of the monomers may be exemplified by 3 mL/1 g, 3.5 mL/1 g, 4 mL/1 g, 4.5 mL/1 g, 5 mL/1 g, 5.5 mL/1 g, etc.
In a specific embodiment of the present invention, the initiator comprises a free radical polymer initiator. Further, the initiator includes at least one of azo-type initiator and peroxide initiator. For example, the azo initiator includes any one or more of azobisisobutyronitrile and azobisisoheptonitrile; the peroxide initiator includes any one or more of benzoyl peroxide, t-butyl benzoyl peroxide and methyl ethyl ketone peroxide.
In practice, the initiator is used in an amount of 0.5% to 1.5%, such as 1%, of the total mass of the polymerized monomers.
In a specific embodiment of the invention, the temperature of the in situ polymerization reaction is 30-70 ℃; the time of the in-situ polymerization reaction is 20-40 h. Further, during the in-situ polymerization reaction, stirring operation is carried out to ensure that the inorganic nano particles are effectively compositely coated and dispersed in the whole composite material system.
As in various embodiments, the temperature of the in situ polymerization reaction may be exemplified by 30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃,55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, etc.; the time of the in-situ polymerization reaction may be exemplified by 20h, 22h, 24h, 28h, 32h, 36h, 40h, etc.
In a specific embodiment of the invention, a gradient heating mode is adopted in the in-situ polymerization reaction. Further, the gradient heating includes: the temperature is kept at 30-33 ℃ for 1-2 h, 40-43 ℃ for 1-2 h, 50-53 ℃ for 1-2 h and 55-70 ℃ for 17-24 h.
In actual operation, the precursor liquid can be transferred into a closed reaction kettle in advance, and heating treatment is carried out by adopting the gradient heating mode; the precursor solution can be transferred into a closed reaction kettle in advance for inert gas exchange, and the precursor solution is heated at a constant temperature (55-70 ℃) under the atmosphere of inert gas to perform heating treatment. Wherein, the inert gas can be high-purity argon.
In some embodiments of the present invention, the method for preparing the composite material may include the steps of:
(a) Dissolving a first polymerization monomer, a second polymerization monomer and a third polymerization monomer in a solvent in advance, adding an initiator, adding inorganic nano particles after uniform dispersion, and uniformly dispersing to obtain a precursor solution;
(b) Heating the precursor liquid to enable the initiator to initiate in-situ polymerization reaction; and then drying the material after the in-situ polymerization reaction.
In a specific embodiment of the present invention, the inorganic nanoparticles are used in an amount of 0.01% to 20.0%, preferably 0.5% to 5.5%, such as 2%, of the sum of the masses of the first, second and third polymeric monomers in the preparation.
In a specific embodiment of the present invention, before the drying treatment of the material after the in-situ polymerization reaction, the method further includes: purifying the material after the in-situ polymerization reaction; the purification includes: mixing the material after the in-situ polymerization reaction with ethanol water solution, separating out solid, and collecting the solid.
In a specific embodiment of the present invention, the volume ratio of ethanol to water in the aqueous ethanol solution is (2.5-3.5) to 1, such as 3:1.
It is a further object of the present invention to provide a composite gel electrolyte comprising an electrolyte solution and any of the above described composite materials.
The composite gel electrolyte provided by the invention has a certain self-supporting effect after gelation treatment, and can anchor the liquid component in the main body, so that the risk of liquid leakage is greatly reduced, and the safety performance is improved. And the composite gel electrolyte provided by the invention has a higher limiting oxygen index.
In a specific embodiment of the invention, in the composite gel electrolyte, the mass fraction of the composite material is 0.8% -5.0%.
As in the various embodiments, the mass fraction of the composite material in the composite gel electrolyte may be illustratively 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
The electrolyte adopted in the composite gel electrolyte can be conventional existing electrolyte, the composite material and the existing electrolyte can be directly compounded in proportion, gelation treatment is carried out, and the preparation process of the existing battery is not required to be changed.
In particular, the electrolyte may include a nonaqueous organic solvent, a lithium salt, and an additive. Wherein the nonaqueous organic solvent may include any one or more of dimethyl carbonate, methylethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, fluoroethylene carbonate, tetraethylene glycol dimethyl ether, ethylene glycol dimethyl ether, 1, 3-dioxapentacyclic, ethyl acetate, gamma-butyrolactone, 6-caprolactone, acetonitrile and sulfolane; the lithium salt may include LiPF6, liBF 4 At least one of LiBOB, liDFOB, liDFOP, liFSI and LiTFSI; the additive may be any one or more of fluoroethylene carbonate, ethylene carbonate and lithium difluorophosphate. The dosage of each component is adjusted according to the conventional dosage.
When the composite material is used in the composite gel electrolyte, the composite material can be directly used in the existing lithium ion electrolyte and has the characteristics of high efficiency and convenience.
The invention also provides a preparation method of any one of the composite gel electrolyte, which comprises the following steps:
the composite material is dissolved in an electrolyte solution and subjected to gelation treatment.
In a specific embodiment of the present invention, the gelation treatment includes: heating at 45-50 deg.c.
As in the various embodiments, the temperature of the heat treatment may be illustratively 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃,50 ℃, and the like.
In a specific embodiment of the present invention, the time of the heat treatment is 10 to 30 hours.
In actual operation, the operations of dissolving the composite material in the electrolyte and gelling treatment may be carried out continuously or separately; for example, the composite material may be dissolved in an electrolyte in advance in proportion, and then injected after the battery is assembled, sealed, and then gelled.
The invention also provides a lithium ion battery, which comprises any one of the composite gel electrolyte.
In the preparation of the lithium ion battery, the existing battery preparation process can be adopted, and the difference is that when the electrolyte is prepared, the composite material is added into the existing electrolyte according to a proportion to obtain a mixture, the obtained mixture is injected, the battery is sealed, and the battery stands still at 45-50 ℃ to complete gelation, so that the corresponding lithium ion battery is obtained.
Example 1
The embodiment provides a preparation method of a composite gel electrolyte, which comprises the following steps:
(1) Dimethyl carbonate and ethyl methyl carbonate were weighed in a glove box in a volume ratio of 1:1, according to a molar ratio of glycidyl acrylate to 3-cyclopentylacrylonitrile of 1.37: 1. glycidyl acrylate and 4arm-PEG Maleimide (four-arm PEG Maleimide, mw=5000 Da) in a mass ratio of 40:1, weighing and fully mixing reaction monomers, wherein the volume ratio of the total mass of the monomers to the solvent is 1g to 3.73mL, then adding an initiator azodiisobutyronitrile (the dosage is 1wt% of the total mass of each monomer), and after the initiator is uniformly dispersed, adding POSS (polyhedral oligomeric silsesquioxane) to obtain a precursor solution; wherein the amount of POSS is 2wt% of the total mass of the monomers.
(2) Heating the precursor liquid obtained in the step (1) to 55 ℃ and stirring for reaction for 24 hours, then pre-freezing the reacted material for 4 hours, and then putting the material into a freeze dryer for freeze drying treatment for 18 hours to obtain the composite material PreCGPN.
(3) Dissolving the composite material PreCGPN obtained in the step (2) in electrolyte, and stirring and dispersing to obtain a mixture; wherein, in the mixture, the mass fraction of the composite material PreCGPN is 2wt%. And then heating the mixture at 45 ℃ for 20 hours to obtain the composite gel electrolyte CGPN.
Wherein the electrolyte may be a commercial electrolyte, such as an electrolyte comprising a solvent, a lithium salt, and an additive; the solvent is ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with the volume ratio of 1:1:1; the lithium salt is LiPF 6 The concentration is about 1.1mol/L, the additive is fluoroethylene carbonate, and the mass fraction of the fluoroethylene carbonate in the electrolyte is 2wt%.
As shown in fig. 2, which is an optical photograph of the composite gel electrolyte prepared in example 1 of the present invention, it is apparent from the figure that the composite gel electrolyte obtained by the gelation treatment of the present invention has a certain self-supporting property.
Example 2
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: inorganic nano-ions are different in kind. In this example, POSS in step (1) was replaced with equal mass halloysite.
Example 3
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the proportions of monomers are different. In this example, the relative proportions of glycidyl acrylate, 3-cyclopentylacrylonitrile and 4arm-PEG maleimid (four-arm PEG Maleimide, mw=5000 Da) are as follows: the molar ratio of 3-cyclopentylacrylonitrile is 1: glycidyl acrylate: the mass ratio of the 4arm-PEG maleimid is 30:1.
example 4
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the proportions of monomers are different. In this example, the relative proportions of glycidyl acrylate, 3-cyclopentylacrylonitrile and 4arm-PEG maleimid (four-arm PEG Maleimide, mw=5000 Da) are as follows: the molar ratio of 3-cyclopentylacrylonitrile is 1: glycidyl acrylate 1.37: the mass ratio of the 4arm-PEG maleimid is 20:1.
example 5
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the monomer types are different. In this example, the 4arm-PEG maleimid (four-arm PEG Maleimide, mw=5000 Da) of step (1) was replaced with an equal mass of 4arm-PEG Acrylate (four-arm PEG Acrylate, mw about 2000 Da).
Example 6
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the monomer types are different. In this example, the glycidyl acrylate in step (1) was replaced with an equimolar amount of glycidyl methacrylate and 3-cyclopentylacrylonitrile was replaced with an equimolar amount of 3- (benzenesulfonyl) acrylonitrile.
Example 7
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the amount of POSS used is different. In this example, POSS was used in an amount of 0.2% by weight based on the total mass of the monomers.
Example 8
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (1), the amount of POSS used is different. In this example, POSS was used in an amount of 20.0% by weight based on the total mass of the monomers.
Example 9
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: and step (2) further comprises a purification treatment before the drying treatment. Specifically, in this embodiment, the precursor solution obtained in the step (1) is heated to 55 ℃ and stirred to react for 24 hours, then the reacted material is mixed with an ethanol water solution (the volume ratio of ethanol to water is 75/25), and after solid is stirred and separated out, the solid is filtered and collected; and then pre-freezing the solid for 4 hours, and then putting the solid into a freeze dryer for freeze drying treatment for 18 hours to obtain the composite material Pre-CGPN.
Example 10
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (3), the amount of the composite material is different. In this example, the mass fraction of the composite PreCGPN in the mixture was 3wt%.
Example 11
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in step (3), the amount of the composite material is different. In this example, the mass fraction of the composite PreCGPN in the mixture was 4wt%.
Example 12
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: the heating treatment modes in the step (2) are different. In this embodiment, step (2) includes: stirring and heating the precursor liquid obtained in the step (1) to 30 ℃ for 1h,40 ℃ for 1h,50 ℃ for 1h,55 ℃ for 21h, pre-freezing the reacted material for 4h, and then putting the pre-frozen material into a freeze dryer for freeze drying for 18h to obtain the composite material PreCGPN.
Example 13
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in the step (3), the addition amounts of the composite material PreCGPN are different. In this example, the amount of the composite PreCGPN was 0.2wt% based on the total mass of the monomers.
Example 14
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in the step (3), the addition amounts of the composite material PreCGPN are different. In this example, the amount of the composite PreCGPN was 10wt% based on the total mass of the monomers.
Example 15
This example provides a method of preparing a composite gel electrolyte, with reference to example 1, differing only in: in the step (3), the addition amounts of the composite material PreCGPN are different. In this example, the amount of the composite PreCGPN was 20wt% based on the total mass of the monomers.
Experimental example 1
Table 1 shows the results of the test of room temperature lithium ion conductivity and Limiting Oxygen Index (LOI) of the composite gel electrolyte materials obtained in the different examples. In the LOI test, the flow rate of the gas is controlled to be 40mm/s, the combustion-supporting gas is oxygen, and the inert gas is nitrogen.
TABLE 1 lithium ion conductivity at room temperature and LOI for different composite gel electrolyte materials
From the test results, the composite gel electrolyte provided by the invention has higher lithium ion conductivity and limiting oxygen index, and can ensure higher lithium ion conductivity and higher limiting oxygen index and improve the safety performance of the material especially aiming at the condition of certain inorganic nano particle dosage.
Experimental example 2
According to the preparation method of the composite gel electrolyte, a mixture of the composite material dissolved in electrolyte is obtained, the battery is assembled, then the mixture is injected, the battery is sealed, and after standing for 12 hours at normal temperature, the composite gel lithium ion battery is obtained after standing for 12 hours at a high temperature of 45 ℃. The charge and discharge test is carried out on each composite gel lithium ion battery at the working voltage of 2.8-4.2V, the current density at the formation stage is 0.2C/0.2C, the charge and discharge current density at the circulation stage is 1.0C/1.0C, and the test results are shown in Table 2.
Wherein, the battery positive electrode adopts ternary material (nickel cobalt manganese ratio is 622), the negative electrode adopts graphite material, the diaphragm adopts PE diaphragm (ceramic surface positive electrode) with single-sided coating, and the battery core liquid injection coefficient is 2.1g/Ah.
Table 2 results of cycle performance test of different composite gel lithium ion batteries
From the test results, the invention can improve the cycle performance of the battery cell by adopting the composite gel lithium ion battery prepared by adding a certain composite material into the electrolyte.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The composite material is characterized by comprising inorganic nano particles and polymers coated on the surfaces of the inorganic nano particles through in-situ polymerization;
the inorganic nanoparticles comprise at least one of POSS and derivatives thereof and halloysite;
the polymerized monomers of the polymer include a first polymerized monomer, a second polymerized monomer, and a third polymerized monomer;
the first polymerization monomer comprises unsaturated olefin compounds containing epoxy groups;
the second polymeric monomer comprises acrylonitrile or a derivative of acrylonitrile;
the third polymeric monomer comprises multi-arm polyethylene glycol maleimide and/or multi-arm polyethylene glycol acrylate.
2. The composite of claim 1, wherein the molar ratio of the first polymerized monomer to the second polymerized monomer is (0.7-2): 1
The mass ratio of the first polymerized monomer to the third polymerized monomer is (2.5-400): 1.
3. the composite of claim 1, wherein the first polymeric monomer comprises any one or more of glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and 2, 3-epoxypropyl acrylate octadecenoic acid;
the second polymeric monomer comprises any one or more of 3-cyclopentylacrylonitrile, 3-phenylacrylonitrile, acrylonitrile, 3- (benzenesulfonyl) acrylonitrile, and 3-ethoxyacrylonitrile;
the third polymeric monomer comprises a four-arm polyethylene glycol maleimide and/or a four-arm polyethylene glycol acrylate.
4. A composite material according to any one of claims 1 to 3, wherein the mass of the inorganic nanoparticles is 0.01% to 20.0%, preferably 0.5% to 5.5% of the sum of the masses of the first, second and third polymeric monomers.
5. A method of producing a composite material according to any one of claims 1 to 4, comprising the steps of:
the first polymerization monomer, the second polymerization monomer, the third polymerization monomer and the inorganic nano particles are subjected to in-situ polymerization reaction in a solvent under the action of an initiator;
and drying the material subjected to the in-situ polymerization reaction.
6. The method of preparing a composite material according to claim 5, wherein the in situ polymerization reaction temperature is 30-70 ℃; the time of the in-situ polymerization reaction is 20-40 h;
preferably, in the in-situ polymerization reaction, a gradient heating mode is adopted;
preferably, the gradient heating includes: the temperature is kept at 30-33 ℃ for 1-2 h, 40-43 ℃ for 1-2 h, 50-53 ℃ for 1-2 h and 55-70 ℃ for 17-24 h.
7. The method of producing a composite material according to claim 5, characterized by having at least one of the following features (1) to (3):
(1) The drying treatment mode comprises the following steps: any one or more of freeze drying, air drying and vacuum drying;
(2) The solvent comprises any one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, diphenyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolactone, acetonitrile and sulfolane;
(3) The initiator includes at least one of azo-type initiator and peroxide initiator.
8. A composite gel electrolyte, characterized by comprising the composite material according to any one of claims 1 to 4 or the composite material prepared by the preparation method according to any one of claims 5 to 7, and an electrolyte;
preferably, in the composite gel electrolyte, the mass fraction of the composite material is 0.8% -5.0%.
9. The method for preparing a composite gel electrolyte according to claim 8, comprising the steps of:
the composite material is dissolved in electrolyte and is subjected to gelation treatment;
preferably, the gelation treatment includes: heating at 45-50 deg.c.
10. A lithium ion battery comprising the composite gel electrolyte of claim 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117174988A (en) * | 2023-09-01 | 2023-12-05 | 哈尔滨工业大学 | Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery |
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| CN117174988A (en) * | 2023-09-01 | 2023-12-05 | 哈尔滨工业大学 | Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery |
| CN117174988B (en) * | 2023-09-01 | 2024-04-30 | 哈尔滨工业大学 | Preparation method of lithium/sodium ion battery material and application of lithium/sodium ion battery material in lithium/sodium ion battery |
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