CN112117487A - Electrolyte material, preparation method thereof, solid electrolyte and battery - Google Patents

Electrolyte material, preparation method thereof, solid electrolyte and battery Download PDF

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CN112117487A
CN112117487A CN201910537156.6A CN201910537156A CN112117487A CN 112117487 A CN112117487 A CN 112117487A CN 201910537156 A CN201910537156 A CN 201910537156A CN 112117487 A CN112117487 A CN 112117487A
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polymer
electrolyte material
molecular weight
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electrolyte
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CN112117487B (en
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康树森
魏彦存
李营
刘岩
范少聪
孟垂舟
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ENN Science and Technology Development Co Ltd
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ENN Science and Technology Development Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses an electrolyte material and a preparation method thereof, a solid electrolyte and a battery, and relates to the technical field of batteries, so that the safety performance of the battery is improved on the premise of ensuring the performance of the battery. The electrolyte material comprises a first polymer as a matrix material, and a second polymer and a metal ion salt dispersed in the matrix material, wherein the first polymer is at least partially compatible with the second polymer, and the molecular weight of the first polymer is larger than that of the second polymer. The electrolyte material, the preparation method thereof, the solid electrolyte and the battery provided by the invention are used in a solid battery.

Description

Electrolyte material, preparation method thereof, solid electrolyte and battery
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte material and a preparation method thereof, a solid electrolyte and a battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. The material has the characteristics of higher energy density, good cycle performance, no memory effect and the like, and becomes the focus of attention of researchers in recent years.
However, the cost of lithium ion batteries has been high due to the lack of lithium resources, and there is a trend toward a new trend. In order to reduce the manufacturing cost of lithium ion batteries, research and development are being carried out on secondary batteries using low-cost elements such as sodium, magnesium, aluminum and the like, and particularly, aluminum ion batteries have the advantages of high storage capacity, high electron gaining and losing number, low cost and the like, and become novel batteries for replacing lithium ion batteries.
Disclosure of Invention
The invention aims to provide an electrolyte material, a preparation method thereof, a solid electrolyte and a battery, so as to improve the safety performance of the battery on the premise of ensuring the performance of the battery.
In order to achieve the above object, the present invention provides an electrolyte material comprising a first polymer as a matrix material, the first polymer being at least partially compatible with a second polymer, the molecular weight of the first polymer being greater than the molecular weight of the second polymer, and a metal ion salt dispersed in the matrix material.
Compared with the prior art, the electrolyte material provided by the invention not only comprises the first polymer used for preparing the matrix, but also comprises the second polymer and the metal ion salt which are mixed together with the first polymer, wherein the first polymer and the second polymer are partially or completely compatible, so that the first polymer and the second polymer can mutually accommodate to form a mixed system with better dispersity and uniformity, and meanwhile, after the first polymer is compatible with the second polymer, the regularity of the internal structure of the matrix formed by the first polymer is reduced due to the fact that the molecular weight of the second polymer is lower than that of the first polymer, so that the crystallinity of the matrix formed by the first polymer is effectively reduced, and the range of an amorphous region of the matrix is enlarged. The process of ion conduction is mainly carried out in the amorphous area of the matrix, so that the dynamic diffusion capacity of metal ions in the electrolyte material is greatly increased under the action of current of the solid electrolyte prepared from the electrolyte material provided by the invention, and the transmission of the metal ions in the matrix is improved.
In addition, the second polymer can control the crystallinity of the first polymer, so that the second polymer can be used as a plasticizer to enable the solid electrolyte formed by solidifying the electrolyte material to have better elasticity and toughness when the solid electrolyte material is manufactured. Meanwhile, because the second polymer has atoms with certain electronegativity, when the solid electrolyte made of the electrolyte material has no current, the electronegativity atoms on the second polymer interact with the metal ions, so that the stability of the metal ions can be effectively ensured, and the metal ions interacting with the electronegativity atoms on the second polymer can be separated from the electronegativity atoms on the second polymer under the action of an electric field and then migrate to the electronegativity atoms on the other second polymer or the electronegativity atoms on the first polymer, so that the metal ions finish migration under the action of the electric field in a reciprocating manner.
Therefore, the metal ions contained in the electrolyte material provided by the invention can be rapidly conducted through the matrix, so that the conductivity of the solid electrolyte is effectively improved, and the solid electrolyte prepared from the electrolyte material can be applied to a battery, so that the danger of electrolyte leakage and even explosion can not occur on the premise of ensuring that the battery has good performance.
The invention also provides a preparation method of the electrolyte material, which is characterized by comprising the following steps:
uniformly mixing metal ion salt, a first polymer and a second polymer in an organic solvent to obtain a mixed solution; removing the organic solvent contained in the mixed solution to obtain an electrolyte material.
Compared with the prior art, the preparation method of the electrolyte material provided by the invention has the same beneficial effects as the electrolyte material provided by the technical scheme, and the details are not repeated herein.
The invention also provides a solid electrolyte which comprises the electrolyte material.
Compared with the prior art, the beneficial effects of the solid electrolyte provided by the invention are the same as those of the electrolyte material provided by the technical scheme, and the details are not repeated herein.
The invention also provides a battery which comprises the solid electrolyte.
Compared with the prior art, the beneficial effects of the battery provided by the invention are the same as those of the solid electrolyte in the technical scheme, and are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flowchart of a method for producing an electrolyte material according to an embodiment 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 existing sodium, potassium and aluminum plasma batteries are receiving increasing attention as a low-cost battery. For example: the sodium ion battery includes an anode and a cathode for intercalating/deintercalating sodium ions, a separator for physically preventing internal short circuits, and an organic liquid electrolyte through which sodium ions are transferred, or a solid electrolyte for both functions. The sodium ion battery has the advantages of abundant and easily-obtained raw materials, low cost, wide distribution and the like. In addition, sodium in the battery system can not generate electrochemical alloying reaction with aluminum, so that the sodium ion battery can adopt aluminum foil as a negative current collector, can effectively avoid the problem of current collector oxidation caused by over-discharge, is beneficial to the safety of the battery, and achieves the aim of further reducing the cost of the battery. From many perspectives, sodium ion batteries have great potential for commercialization and sustainable use. Therefore, it is required to develop a solid organic polymer electrolyte for a sodium, potassium, aluminum plasma battery, which provides a solid ion battery with low cost and high stability, and particularly to develop a method for preparing a solid organic polymer electrolyte to improve the conductivity thereof and improve the overall performance of the battery.
The electrolyte material provided by the embodiment of the invention comprises a first polymer serving as a matrix material, and a second polymer and a metal ion salt which are dispersed in the matrix material, wherein the first polymer is at least partially compatible with the second polymer, and the molecular weight of the first polymer is larger than that of the second polymer.
When the electrolyte material is prepared, the first polymer, the second polymer and the metal ion salt can be mixed in the organic solvent, so that the mutual contact area among the first polymer, the second polymer and the metal ion salt is increased, the compatibility of the second polymer and the first polymer and the interaction between the second polymer and the metal ion are promoted, the transmission and stability of the metal ion are improved, and meanwhile, the regularity of the internal structure of a matrix formed by the first polymer is reduced, and the crystallinity of the matrix formed by the first polymer is effectively reduced.
The electrolyte material provided by the invention comprises a first polymer used for preparing a matrix, and also comprises a second polymer and a metal ion salt which are mixed together with the first polymer, wherein the first polymer and the second polymer are partially or completely compatible, so that the first polymer and the second polymer can mutually accommodate to form a mixed system with better dispersity and uniformity, and meanwhile, after the first polymer and the second polymer are compatible, the regularity of the internal structure of the matrix formed by the first polymer is reduced due to the fact that the molecular weight of the second polymer is lower than that of the first polymer, so that the crystallinity of the matrix formed by the first polymer is effectively reduced, and the range of an amorphous region of the matrix is enlarged. The process of ion conduction is mainly carried out in the amorphous area of the matrix, so that the dynamic diffusion capacity of metal ions in the electrolyte material is greatly increased under the action of current of the solid electrolyte prepared from the electrolyte material provided by the invention, and the transmission of the metal ions in the matrix is improved.
In addition, the second polymer can control the crystallinity of the first polymer, so that the second polymer can be used as a plasticizer to enable the solid electrolyte formed by solidifying the electrolyte material to have better elasticity and toughness when the solid electrolyte material is manufactured. Meanwhile, due to the existence of atoms with certain electronegativity on the second polymer, when no current flows in the solid electrolyte made of the electrolyte material, the electronegativity atoms on the second polymer interact with metal ions, so that the stability of the metal ions can be effectively ensured; therefore, compared with the prior art, the dynamic diffusion capacity of the metal ions of the electrolyte material provided by the invention is greatly increased, and the conductivity requirement of a solid electrolyte can be met.
Therefore, the metal ions contained in the electrolyte material provided by the invention can be rapidly conducted through the matrix, so that the conductivity of the solid electrolyte is effectively improved, and the solid electrolyte prepared from the electrolyte material can be applied to a battery, so that the danger of electrolyte leakage and even explosion can not occur on the premise of ensuring that the battery has good performance.
It should be noted that the above metal ion salt may include an aluminum ion salt, an alkali metal ion salt, or a magnesium ion salt, but is not limited thereto. The alkali metal ion salt includes an aluminum ion salt, an alkali metal ion salt or a magnesium ion salt, but is not limited thereto.
The aluminum ion salt is prepared by mixing one or more of aluminum chloride, aluminum nitrate, aluminum sec-butoxide and aluminum trifluoromethanesulfonate in any proportion. The magnesium ion salt is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate. The above alkali metal salt ion salt includes a sodium ion salt, a lithium ion salt or a potassium ion salt.
Wherein, the sodium ion salt is one or more of sodium sulfate, sodium chlorate, sodium nitrate or sodium trifluoromethanesulfonate, the lithium ion salt is one or more of lithium sulfate, lithium chloride and lithium trifluoromethanesulfonate, and the potassium ion salt is one or more of potassium sulfate, potassium nitrate and potassium chlorate.
In some embodiments, when the electrolyte material is made into a solid electrolyte, the solid electrolyte is not sensitive to water and oxygen, and the battery assembly can be carried out in the air, so that the investment caused by environmental control is greatly reduced. Further, the first polymer and the second polymer are both organic polymers, and these organic polymers are generally plasticized polymers. At the moment, the electrolyte material can be made into solid electrolytes in various shapes according to actual requirements, and the plasticized matrix generally has good hydrophobicity, so that the solid electrolyte made of the electrolyte material has better anti-water-oxygen performance. Specifically, the first polymer can be one or a mixture of a plurality of polyethylene glycol, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone and poly (vinylidene fluoride-co-hexafluoropropylene) in any proportion, and the listed film forming materials have good water and oxygen resistance, so that the solid electrolyte prepared from the electrolyte material has better water and oxygen resistance. In addition, the molecular weight of the first polymer was 5X 105g/mol～1×106g/mol, thereby leading the prepared matrix to have the function of supporting and stabilizing.
The second polymer is one or more of polyethylene glycol, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone and polyvinylidene fluoride-co-hexafluoropropylene mixed at any ratio, but is not limited thereto. In addition, the molecular weight of the second polymer is 400 g/mol-20000 g/mol, so that the second mixture and the first polymer are uniformly mixed, and the crystallinity of a matrix formed by the first polymer is effectively reduced. Among these polymers, polyethylene glycol has the best solubility, is easily soluble in oily solvents and miscible with aqueous solvents, and has good compatibility with most of the first polymers, so that the solid electrolyte prepared from polyethylene glycol has the best conductive effect.
In some embodiments, if the metal ion salt is less, the conductivity of the solid state electrolyte made of the electrolyte material will be lower; therefore, the molar weight of the metal ion salt is 5 to 30 percent of the molar weight of the first polymer, and the prepared solid electrolyte prepared from the electrolyte material has higher conductivity and meets the requirement of a battery on the electrolyte.
In some embodiments, the strength of the electrolyte membrane is reduced by using a higher amount of the second polymer, and the crystallinity of the first polymer is not controlled significantly by the second polymer when the amount of the second polymer is lower, and the crystallinity of the solid electrolyte made of the corresponding electrolyte material is not controlled well, based on that the mass ratio of the first polymer to the second polymer is 1: (0.1-0.4) so that the solid electrolyte made of the electrolyte material has low crystallinity, metal ions can rapidly migrate in the solid electrolyte, and the ionic conductivity is high. Meanwhile, when the crystallinity of the solid electrolyte is reduced, the solid electrolyte has good toughness and mechanical strength, so that the environmental adaptability of the solid electrolyte is better.
As shown in fig. 1, an embodiment of the present invention further provides a method for preparing the above electrolyte material, where the method for preparing the electrolyte material includes:
step S100: and uniformly mixing the metal ion salt, the first polymer and the second polymer in an organic solvent to obtain a mixed solution.
Step S200: and removing the organic solvent contained in the mixed solution to obtain the electrolyte material.
Compared with the prior art, the beneficial effects of the preparation method of the electrolyte material provided by the embodiment of the invention are the same as those of the electrolyte material provided by the embodiment, and are not repeated herein. In addition, as the first polymer, the second polymer and the metal ion salt can be dissolved in the organic solvent, the first polymer, the second polymer and the metal ion salt are mixed in the organic solvent, so that the mutual contact area of the first polymer, the second polymer and the metal ion salt is increased, the interaction between the second polymer and the metal ion can be promoted, the transmission and the stability of the metal ion are improved, meanwhile, the second polymer and the first polymer are fully and uniformly mixed, the crystallinity of the first polymer is effectively reduced, the range of an amorphous region of a matrix formed by the first polymer is increased, and the process of ion conduction is mainly carried out in the amorphous region of the matrix, so that the transmission of the metal ion in the matrix is improved.
It is understood that the specific types and amounts of the first polymer, the second polymer and the metal ion salt used in the preparation method of the electrolyte material can be referred to the foregoing, and are not described herein again.
In some embodiments, the organic solvent is one or more of acetone, butyl ester, glycerol, pyridine, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
In some embodiments, the uniformly mixing the metal ion salt, the first polymer, and the second polymer in the organic solvent in consideration of the solubility of the first polymer, the metal ion salt, and the second polymer in the organic solvent to obtain the mixed solution includes:
mixing the first polymer, the second polymer and the metal ion salt in an organic solvent at the temperature of 20-80 ℃, wherein the total mass of the metal ion salt, the first polymer and the second polymer contained in each milliliter of mixed solution is 80-100 mg, and the formed mixed solution has moderate viscosity and cannot be too viscous due to excessive metal ion salt, the first polymer and the second polymer, so that the material cannot be doped unevenly; and the problem that the film forming of the electrolyte material is poor due to long time for removing the solvent because the viscosity is too low because the metal ion salt, the first polymer and the second polymer are too little is avoided.
In addition, the first polymer, the second polymer and the metal ion salt are mixed uniformly in the organic solvent, and a stirrer may be used. The first polymer, the second polymer, the metal ion salt and the organic solvent are placed in a stirrer and stirred at the temperature of 20-80 ℃ to ensure that the obtained mixed solution is uniform and stable.
In some embodiments, the removing the organic solvent contained in the mixed solution to obtain the electrolyte material includes:
and (3) evaporating the organic solvent contained in the mixed solution at 40-110 ℃ to obtain the electrolyte material. When the organic solvent contained in the mixed solution is distilled off at 40 to 110 ℃, the solvent can be gradually distilled off from the mixed solution, and the interaction between the electronegative atoms and the metal ions contained in the second polymer is not affected. The glove box is laboratory equipment which fills high-purity inert gas into the box body and filters active substances in the box body in a circulating mode, and is widely applied to an anhydrous, oxygen-free and dust-free ultra-pure environment, so that organic solvent evaporation is preferably carried out in the glove box for drying or airing, and electrolyte materials are prevented from being oxidized.
The embodiment of the invention also provides a solid electrolyte which comprises the electrolyte material.
Compared with the prior art, the beneficial effects of the solid electrolyte provided by the embodiment of the invention are the same as those of the electrolyte material provided by the embodiment, and are not repeated herein.
The embodiment of the invention also provides a battery which comprises the solid electrolyte.
Compared with the prior art, the beneficial effects of the battery provided by the embodiment of the invention are the same as those of the electrolyte material provided by the embodiment, and are not repeated herein.
In order to demonstrate that the conductivity of the electrolyte material is relatively high, the electrolyte material provided by the embodiments of the present invention is described in detail below, and the following description is only for explanation and is not limited thereto.
Example one
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 5X 10 at 20 ℃ using a stirrer5Uniformly stirring g/mol polyethylene glycol, polyethylene glycol with the molecular weight of 400g/mol and aluminum chloride in acetone to obtain a mixed solution; wherein the molecular weight is 5 × 105The mass ratio of the g/mol polyethylene glycol to the polyethylene glycol with the molecular weight of 400g/mol is 1: 0.1, molecular weight 5X 105The molar ratio of the g/mol of polyethylene glycol to the aluminum chloride is 1: 0.05 aluminum chloride, 5X 10 molecular weight per ml of mixed solution5The total mass of the polyethylene glycol and the polyethylene glycol with the molecular weight of 400g/mol is 80 mg.
Step S200: and drying acetone contained in the mixed solution at 56 ℃ by using a glove box to obtain the electrolyte material.
Comparative example 1
The first step is as follows: the molecular weight is 5X 10 at 20 ℃ using a stirrer5Uniformly stirring g/mol polyethylene glycol and aluminum chloride in acetone to obtain a mixed solution; wherein the molecular weight is 5 × 105The molar ratio of the g/mol of polyethylene glycol to the aluminum chloride is 1: 0.05, aluminum chloride and 5X 10 molecular weight/ml of mixed solution5g/mol is the total mass of the polyethylene glycol of 80 mg.
The second step is that: and drying acetone contained in the mixed solution at 56 ℃ by using a glove box to obtain the electrolyte material.
At this time, the electrolyte material obtained in example one and the electrolyte material obtained in comparative example one were subjected to an ion conductivity test, respectively, and the ion conductivity of the electrolyte material obtained in example one was 1.6 × 10-5S/cm, ion conductivity of the electrolyte material obtained in comparative example one was 7.5X 10-6S/cm. Therefore, the electrolyte material obtained by the preparation method of the embodiment of the inventionAs the low molecular weight polyethylene glycol is doped in the matrix, the ionic conductivity is greatly improved.
Example two
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 1X 10 at 80 ℃ using a stirrer6Uniformly stirring g/mol polyvinylidene fluoride, polyethylene glycol with the molecular weight of 20000g/mol and aluminum nitrate in pyridine to obtain a mixed solution; wherein the molecular weight is 1 × 106The mass ratio of g/mol polyvinylidene fluoride to polyethylene glycol with the molecular weight of 20000g/mol is 1: 0.1, molecular weight 1X 106The molar ratio of g/mol polyvinylidene fluoride to aluminum nitrate is 1: 0.05 aluminum nitrate contained in the mixed solution per ml, molecular weight 1X 106g/mol is 100mg of the total mass of the polyvinylidene fluoride and the polyethylene glycol with the molecular weight of 20000 g/mol.
Step S200: and drying pyridine contained in the mixed solution at 40 ℃ by using a glove box to obtain the electrolyte material.
Comparative example No. two
The first step is as follows: the molecular weight is 1X 10 at 80 ℃ using a stirrer6Uniformly stirring g/mol polyvinylidene fluoride and aluminum nitrate in pyridine to obtain a mixed solution; wherein the molecular weight is 1 × 106The molar ratio of g/mol polyvinylidene fluoride to aluminum nitrate is 1: 0.05 aluminum nitrate and 1X 10 molecular weight per ml of the mixed solution6g/mol is 100mg of the total mass of the polyvinylidene fluoride.
The second step is that: and drying pyridine contained in the mixed solution at 40 ℃ by using a glove box to obtain the electrolyte material.
At this time, the electrolyte material obtained in example two and the electrolyte material obtained in comparative example two were subjected to an ion conductivity test, respectively, and the ion conductivity of the electrolyte material obtained in example two was 2.3 × 10-5S/cm, the ionic conductivity of the electrolyte material obtained in comparative example II was 6.3X 10-6S/cm. Therefore, the electrolyte material obtained by the preparation method of the embodiment of the invention has the advantages that the low molecular weight polyethylene glycol is doped in the matrix, and the ionic conductivity is highThe rate is greatly improved.
EXAMPLE III
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 6X 10 at 40 ℃ using a stirrer5Uniformly stirring g/mol polymethyl methacrylate, polyethylene glycol with the molecular weight of 800g/mol and aluminum trifluoromethanesulfonate in tetrahydrofuran to obtain a mixed solution; wherein the molecular weight is 6 × 105The mass ratio of the g/mol polymethyl methacrylate to the polyethylene glycol with the molecular weight of 800g/mol is 1: 0.1, molecular weight 6X 105The molar ratio of the g/mol of polymethyl methacrylate to the aluminum trifluoromethanesulfonate was 1: 0.05 aluminum triflate, molecular weight 6X 10, contained per ml of mixed solution5The total mass of the polymethyl methacrylate and the polyethylene glycol with the molecular weight of 800g/mol is 90 mg.
Step S200: and drying tetrahydrofuran contained in the mixed solution at 110 ℃ by using a glove box to obtain the electrolyte material.
Comparative example No. three
The first step is as follows: the molecular weight is 6X 10 at 40 ℃ using a stirrer5Uniformly stirring g/mol of polymethyl methacrylate and aluminum trifluoromethanesulfonate in tetrahydrofuran to obtain a mixed solution; wherein the molecular weight is 6 × 105The molar ratio of the g/mol of polymethyl methacrylate to the aluminum trifluoromethanesulfonate was 1: 0.05 aluminum triflate per ml of the mixture and a molecular weight of 6X 105g/mol is the total mass of the polymethyl methacrylate of 90 mg.
The second step is that: and drying tetrahydrofuran contained in the mixed solution at 110 ℃ by using a glove box to obtain the electrolyte material.
At this time, the electrolyte material obtained in example three and the electrolyte material obtained in comparative example three were each subjected to an ion conductivity test, and the ion conductivity of the electrolyte material obtained in example three was 1.1 × 10-4S/cm, the ionic conductivity of the electrolyte material obtained in comparative example III was 2X 10-5S/cm. Therefore, the electrolyte material obtained by the preparation method of the embodiment of the invention is prepared byThe low molecular weight polyethylene glycol material is doped in the matrix, so that the ionic conductivity is greatly improved.
Example four
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 6X 10 at 40 ℃ using a stirrer5Uniformly stirring g/mol polyvinyl alcohol, polyvinylidene fluoride with the molecular weight of 10000g/mol and sodium sulfate in glycerol to obtain a mixed solution; wherein the molecular weight is 6 × 105The mass ratio of the g/mol polyvinyl alcohol to the polyvinylidene fluoride with the molecular weight of 10000g/mol is 1: 0.15, molecular weight 6X 105The molar ratio of the g/mol polyvinyl alcohol to the sodium sulfate is 1: 0.1, sodium sulfate contained in the mixed solution per ml, molecular weight 6X 105The total mass of polyvinyl alcohol in g/mol and polyvinylidene fluoride in 10000g/mol is 88 mg.
Step S200: and drying the glycerol contained in the mixed solution at 90 ℃ by using a glove box to obtain the electrolyte material.
EXAMPLE five
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 7X 10 at 50 ℃ using a stirrer5Uniformly stirring g/mol polyvinylpyrrolidone, polymethyl methacrylate with the molecular weight of 1000g/mol and lithium sulfate in nitrogen-methyl pyrrolidone to obtain a mixed solution; wherein the molecular weight is 7 × 105The mass ratio of the g/mol polyvinylpyrrolidone to the polymethyl methacrylate with the molecular weight of 1000g/mol is 1: 0.2, molecular weight 7X 105The molar ratio of g/mol polyvinylpyrrolidone to lithium sulfate is 1: 0.15, lithium sulfate contained in the mixed solution per ml, molecular weight 7X 105The total mass of polyvinylpyrrolidone and polymethyl methacrylate in g/mol was 82 mg.
Step S200: and drying the nitrogen-methyl pyrrolidone contained in the mixed solution at 70 ℃ by using a glove box to obtain the electrolyte material.
EXAMPLE six
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 8X 10 at 60 ℃ using a stirrer5Uniformly stirring g/mol polyvinylidene fluoride-co-hexafluoropropylene, polyvinyl alcohol with the molecular weight of 8000g/mol, sodium nitrate and sodium chloride in N, N-dimethylacetamide to obtain a mixed solution; wherein the molecular weight is 8 × 105The mass ratio of g/mol polyvinylidene fluoride-co-hexafluoropropylene to 8000g/mol polyvinyl alcohol is 1: 0.15, molecular weight 8X 105The total molar ratio of g/mol polyvinylidene fluoride-co-hexafluoropropylene to sodium nitrate and sodium chloride was 1: 0.2, sodium nitrate, sodium chloride, molecular weight 8X 10 contained in each ml of mixed solution5The total mass of polyvinylidene fluoride-co-hexafluoropropylene in g/mol and polyvinyl alcohol in 8000g/mol was 98 mg.
Step S200: and drying the N, N-dimethylacetamide contained in the mixed solution at 65 ℃ by using a glove box to obtain the electrolyte material.
EXAMPLE seven
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight was 9X 10 at 56 ℃ using a stirrer5Uniformly stirring g/mol polyethylene glycol, 8000g/mol polyvinyl alcohol and magnesium chloride in acetonitrile to obtain a mixed solution; wherein the molecular weight is 9 × 105The mass ratio of the g/mol polyethylene glycol to the polyvinyl alcohol with the molecular weight of 8000g/mol is 1: 0.25, molecular weight 9X 105The molar ratio of the g/mol polyethylene glycol to the magnesium chloride is 1: 0.25, magnesium chloride contained in the mixed solution per ml, molecular weight 9X 105The total mass of polyethylene glycol and 8000g/mol of polyvinyl alcohol is 86 mg.
Step S200: and drying acetonitrile contained in the mixed solution at 78 ℃ by using a glove box to obtain the electrolyte material.
Example eight
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: benefit toWith a stirrer, the molecular weight is 5X 10 at 42 DEG C5Uniformly stirring g/mol polyethylene glycol, polyvinylpyrrolidone with the molecular weight of 4000g/mol and magnesium chloride in butyl ester to obtain a mixed solution; wherein the molecular weight is 5 × 105The mass ratio of the g/mol polyethylene glycol to the polyvinylpyrrolidone with the molecular weight of 4000g/mol is 1: 0.4, molecular weight 5X 105The molar ratio of the g/mol polyethylene glycol to the magnesium chloride is 1: 0.3, magnesium chloride contained in the mixed solution per ml, molecular weight 5X 105The total mass of polyethylene glycol and polyvinylpyrrolidone in g/mol was 96mg and 4000 g/mol.
Step S200: and drying butyl ester contained in the mixed solution at 68 ℃ by using a glove box to obtain the electrolyte material.
Example nine
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 5X 10 at 36 ℃ using a stirrer5Uniformly stirring g/mol polyethylene glycol, polyvinylidene fluoride-co-hexafluoropropylene with the molecular weight of 5000g/mol and magnesium nitrate in butyl ester to obtain a mixed solution; wherein the molecular weight is 5 × 105The mass ratio of the g/mol polyethylene glycol to the polyvinylidene fluoride-co-hexafluoropropylene with the molecular weight of 5000g/mol is 1: 0.1, molecular weight 5X 105The molar ratio of the g/mol polyethylene glycol to the magnesium nitrate is 1: 0.3 magnesium nitrate, 5X 10 molecular weight, per ml of mixed solution5The total mass of polyethylene glycol in g/mol and polyvinylidene fluoride-co-hexafluoropropylene in a concentration of 5000g/mol was 85 mg.
Step S200: and drying butyl ester contained in the mixed solution at 69 ℃ by using a glove box to obtain the electrolyte material.
Example ten
The preparation method of the electrolyte material provided by the embodiment of the invention comprises the following steps:
step S100: the molecular weight is 8X 10 at 72 ℃ using a stirrer5Uniformly stirring g/mol polyethylene glycol, polyethylene glycol with molecular weight of 2000g/mol and potassium nitrate in glycerol to obtain a mixed solution; wherein, the molecular weight is 8105The mass ratio of the g/mol polyethylene glycol to the polyethylene glycol with the molecular weight of 2000g/mol is 1: 0.2, molecular weight 5X 105The molar ratio of the polyethylene glycol to the potassium nitrate is 1: 0.2, potassium nitrate contained in the mixed solution per ml, molecular weight 8X 105The total mass of polyethylene glycol in g/mol and 2000g/mol was 80 mg.
Step S200: and drying the glycerol contained in the mixed solution at 100 ℃ by using a glove box to obtain the electrolyte material.
The electrolyte material prepared by the method for preparing the electrolyte material provided in the above example was prepared as a solid electrolyte, and the conductivity of the solid electrolyte was measured, and the measurement results are shown in table 1.
Table 1 list of ionic conductivities of solid electrolytes
Examples Ionic conductivity/S/cm
A 1.6×10-5
II 2.3×10-5
III 1.1×10-4
As can be seen from table 1, after the electrolyte material provided in the embodiment of the present invention is made into a solid electrolyte, the maximum ionic conductivity of the solid electrolyte can reach 10-4The grade of S/cm can meet the electrolyte requirement of the battery. Therefore, the embodiments of the present invention provideThe provided electrolyte material and the solid electrolyte prepared by the electrolyte material can be used in batteries.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. An electrolyte material comprising a first polymer as a matrix material, said first polymer being at least partially compatible with a second polymer and a metal ion salt dispersed in said matrix material, said first polymer having a molecular weight greater than the molecular weight of said second polymer.
2. The electrolyte material of claim 1,
the molecular weight of the first polymer is 5 x 105g/mol～1×106g/mol；
And/or the presence of a gas in the gas,
the molecular weight of the second polymer is 400 g/mol-20000 g/mol;
and/or the presence of a gas in the gas,
the metal ion salt is alkali metal ion salt, magnesium ion salt or aluminum ion salt.
3. The electrolyte material of claim 1 wherein the first polymer and the second polymer are both plasticizable polymers.
4. The electrolyte material as claimed in any one of claims 1 to 3, wherein the first polymer comprises one or more of polyethylene glycol, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinylidene fluoride-co-hexafluoropropylene mixed at any ratio;
and/or the second polymer is prepared by mixing one or more of polyethylene glycol, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone and polyvinylidene fluoride-co-hexafluoropropylene in any proportion.
5. The electrolyte material according to any one of claims 1 to 3, wherein the mass ratio of the first polymer to the second polymer is 1: (0.1-0.4), wherein the molar ratio of the first polymer to the metal ion salt is 1: (0.05-0.3).
6. A method for producing the electrolyte material according to any one of claims 1 to 5, characterized by comprising:
uniformly mixing metal ion salt, a first polymer and a second polymer in an organic solvent to obtain a mixed solution;
removing the organic solvent contained in the mixed solution to obtain an electrolyte material.
7. The method for producing the electrolyte material according to claim 6, wherein the mixed solution contains the metal ion salt, the first polymer, and the second polymer in a total mass of 80mg to 100mg per ml; and/or the presence of a gas in the gas,
the removing the organic solvent contained in the mixed solution to obtain the electrolyte material includes:
and (3) evaporating the organic solvent contained in the mixed solution at 40-110 ℃ to obtain the electrolyte material.
8. The method of claim 6, wherein the organic solvent is one or more selected from acetone, butyl ester, glycerol, pyridine, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, and N, N-dimethylacetamide.
9. A solid electrolyte comprising the electrolyte material according to any one of claims 1 to 5 or the electrolyte material produced by the method for producing an electrolyte material according to any one of claims 6 to 8.
10. A battery comprising the solid electrolyte according to claim 9.
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