CN116666738A - Solid electrolyte for sodium ion battery and preparation method thereof - Google Patents

Solid electrolyte for sodium ion battery and preparation method thereof Download PDF

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Publication number
CN116666738A
CN116666738A CN202310960687.2A CN202310960687A CN116666738A CN 116666738 A CN116666738 A CN 116666738A CN 202310960687 A CN202310960687 A CN 202310960687A CN 116666738 A CN116666738 A CN 116666738A
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sodium ion
electrolyte
layer
polymer
ion battery
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CN116666738B (en
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王波
王检
张迪
李昭进
王秋君
杨振
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Ji Guangyi
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Hebei University of Science and Technology
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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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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 relates to the technical field of energy storage, and particularly discloses a solid electrolyte for a sodium ion battery and a preparation method thereof. The solid electrolyte for the sodium ion battery comprises a metal organic frame layer, a transition layer and a polymer electrolyte layer which are sequentially formed on the surface of an electrode; wherein the material of the metal organic framework layer comprises a sodium ion electrolyte, a metal organic framework material and a first polymer; the metal organic framework layer and the polymer electrolyte layer are mutually penetrated to form the transition layer; the material of the polymer electrolyte layer includes a sodium ion electrolyte, a crosslinking agent, and a second polymer. The solid electrolyte provided by the invention is a novel mixed solid electrolyte capable of improving the low-temperature performance of the sodium ion battery, and has a wide voltage window, high ion conductivity, high energy density and stable structural framework through the synergistic effect between three layers, so that the cycling stability and the low-temperature performance of the sodium ion battery are improved.

Description

Solid electrolyte for sodium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage, in particular to a solid electrolyte for a sodium ion battery and a preparation method thereof.
Background
Compared with the lithium ion battery widely applied at present, the sodium ion battery is a novel renewable energy storage technology, has the advantages of rich sodium elements, low cost, high energy density and the like, and is a potential energy storage solution. In addition, the sodium ion battery has higher cycle life and better safety performance, and can play an important role in a renewable energy system. With the increasing global demand for clean energy and sustainable development, the development of high-performance sodium ion batteries is of great importance. Therefore, not only is the energy density and power density of the sodium ion battery required to be increased, but also the ability thereof to adapt to extreme working environments due to regional and seasonal differences is further required.
However, when the sodium ion battery is operated at a low temperature of below-30 ℃, the problems of serious capacity fade, short cycle life, difficult charging and the like often exist, and researches show that the low temperature performance of the sodium ion battery has an obvious relationship with the electrolyte. Electrolytes for sodium ion batteries include liquid electrolytes and solid electrolytes. Among them, the liquid electrolyte has potential safety hazard due to the use of volatile and flammable organic solvents. The solid electrolyte does not have the above problems, and mainly includes an inorganic solid electrolyte and a polymer solid electrolyte. However, both the liquid electrolyte and the solid electrolyte have the defects of limited capacity exertion, poor cycle stability and rate performance and the like in a low-temperature environment below-30 ℃ and influence the exertion of the electrochemical performance of the sodium ion battery.
Disclosure of Invention
In view of the above, the present invention provides a solid electrolyte for a sodium ion battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a solid electrolyte for a sodium ion battery includes a metal organic frame layer, a transition layer and a polymer electrolyte layer formed in this order on the surface of an electrode;
wherein the material of the metal organic framework layer comprises a sodium ion electrolyte, a metal organic framework material and a first polymer;
the metal organic framework layer and the polymer electrolyte layer are mutually penetrated to form the transition layer;
the material of the polymer electrolyte layer includes a sodium ion electrolyte, a crosslinking agent, and a second polymer.
Compared with the prior art, the solid electrolyte for the sodium ion battery is a novel mixed solid electrolyte capable of improving the low-temperature performance of the sodium ion battery. The solid electrolyte system has good stability while ensuring high ionic conductivity, is less subject to temperature fluctuation, is more stable at low temperature, and greatly improves the low-temperature electrochemical performance of the battery. The metal organic frame layer is fully contacted with the surface of the electrode, so that Na dendrite growth is reduced, further, the electron and ion transmission efficiency is increased, and the metal organic frame material is introduced as a support column, so that the overall stability and the decomposition resistance of the electrolyte are improved, and the electrolyte has excellent conductivity; the metal organic frame layer and the polymer electrolyte layer are mutually penetrated to form a transition layer, so that the three layers have good chemical compatibility, when two different polymers are contacted, uniform mixture or interface is formed by utilizing the interaction between molecules of the first polymer and the second polymer and the similarity of chemical structures, phase separation or mutual repulsion does not occur, the efficient conduction and diffusion of sodium ions between the metal organic frame layer and the polymer electrolyte layer are realized, and concentration polarization in electrolyte is reduced; the polymer electrolyte layer can serve multiple functions of ion transmission, electron isolation, interface structure stabilization, and overall flexibility and plasticity improvement of the composite electrolyte in electrochemical reaction. Through the synergistic effect of the metal organic framework layer, the transition layer and the polymer electrolyte layer, the electrolyte has a wide voltage window, high ion conductivity, high energy density and stable structural framework, and can be effectively matched with anode and cathode materials at the same time, so that stable contact between the electrolyte and the electrodes is realized, and the cycle stability and low-temperature performance of the sodium ion battery are improved.
Preferably, the metal organic framework layer is a porous film formed by random stacking of nanofibers.
Preferably, the metal organic framework material is at least one of MIL-101, MIL-88A, MIL-88B, UIO-66, PCN-224, MOF-253 or NU-1000.
Preferably, the first polymer is at least one of polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride, polyacrylonitrile, polycaprolactone, polylactic acid, polyethersulfone, polyurethane, or polystyrene.
Preferably, the sodium ion electrolyte is at least one of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium bisoxalato borate or sodium trifluoromethane sulfonate.
Preferably, the second polymer is at least one of a polypropylene ether, a polydimethylsiloxane, a polyvinyl alcohol, a polyethylene oxide, or a polyvinylidene fluoride. Preferably the second polymer can provide a solvent carrier for sodium salt in the composite solid electrolyte, and good contact with the metal organic framework layer is realized through the organic mutual solubility concept, so that efficient transmission of sodium ions between the metal organic framework layer and the polymer electrolyte layer is promoted.
Preferably, the cross-linking agent is at least one of a glycol stearate, a polydiacrylate, a polyvinyl formate, a polyoxymethylene, a divinyl phenol, an ethyl acrylate formaldehyde condensate, stannous chloride, a polyol acrylate, an acrylic unit, an isocyanate, a silicone cross-linking agent, a polydimethylsiloxane cross-linking agent, an epoxy resin, boric acid, or chromic acid.
Preferably, the thickness of the metal organic framework layer is 5-15 μm.
Preferably, the thickness of the transition layer is 5-10 μm.
Preferably, the thickness of the polymer electrolyte layer is 5 μm to 15 μm.
In another aspect, the present invention provides a method for preparing the solid electrolyte for a sodium ion battery, comprising the steps of:
s1, uniformly mixing a sodium ion electrolyte, a metal organic frame material and a first polymer in a solvent, then carrying out electrostatic spinning on the surface of an electrode, carrying out ultraviolet irradiation while carrying out electrostatic spinning, and drying to obtain a metal organic frame layer;
s2, dispersing the sodium ion electrolyte into a second polymer monomer, then adding a cross-linking agent for reaction, and adding the reaction solution to the surface of the metal organic framework layer before the second polymer monomer is completely reacted, so as to completely react, thereby obtaining the solid electrolyte for the sodium ion battery.
Compared with the prior art, the invention adopts electrostatic spinning to load the metal organic frame layer consisting of the metal organic frame material, the sodium ion electrolyte and the first polymer on the electrode, is favorable for the full contact between the surface of the electrode and the electrolyte under the action of electrostatic force, reduces Na dendrite growth, and further increases the electron and ion transmission efficiency; meanwhile, the nanofiber film formed by spinning is exposed to ultraviolet rays to form holes, so that the high porosity can greatly improve the ion transmission power in the electrolyte and reduce the concentration polarization in the electrolyte; the introduction of the metal organic frame material as a support column increases the overall stability and decomposition resistance of the electrolyte, and has excellent conductivity; the addition of the first polymer ensures that the prepared spinning solution smoothly ejects the polymer-coated metal-organic framework material under high pressure, and further stretches the polymer-coated metal-organic framework material in air, adjusts the fiber diameter and inhibits fiber aggregation. And adding the second polymer which is not completely polymerized to the surface of the metal organic framework layer to continue the reaction, so that a transition layer is formed at the interface of the metal organic framework layer and the polymer electrolyte layer. The incompletely polymerized second polymer has good chemical compatibility with the metal organic framework layer, the solid electrolyte system can ensure high ionic conductivity and has good stability, the fluctuation of temperature is small, the polymer is more stable at low temperature, and the low-temperature electrochemical performance of the battery is greatly improved. The invention enables the prepared electrolyte to have wider voltage window, higher ion conductivity, higher energy density and more stable structural framework through the synergistic effect of the metal organic framework layer, the transition layer and the polymer electrolyte layer.
Preferably, in step S1, the wavelength of the ultraviolet light is 20nm to 400nm, and the radiation intensity is0.1mW/cm 2 ~2.0mW/cm 2 。
Preferably, in the step S1, the filament outlet diameter of the electrostatic spinning is 300-500 nm, the voltage is 18-25 kV, the scanning speed is 10-30 mm/S, the injection speed is 5-30 mu L/min, the collecting distance is 6-15 cm, and the rotating speed is 300-800 r/min.
Preferably, the electrode is a hard carbon anode, a transition metal compound anode, a layered oxide cathode or NaVPO 3 And a positive electrode.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
In one aspect, the present invention provides a solid electrolyte for a sodium ion battery comprising a metal organic frame layer, a transition layer and a polymer electrolyte layer formed in sequence on the surface of an electrode;
wherein the raw materials of the metal organic frame layer comprise sodium ion electrolyte, metal organic frame material and first polymer;
the metal organic framework layer and the polymer electrolyte layer are mutually penetrated to form the transition layer;
the raw materials of the polymer electrolyte layer comprise sodium ion electrolyte, a cross-linking agent and monomers used for synthesizing a second polymer.
In some embodiments, the first polymer is at least one of polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride, polyacrylonitrile, polycaprolactone, polylactic acid, polyethersulfone, polyurethane, or polystyrene.
In another aspect, the present invention provides a method for preparing the solid electrolyte for a sodium ion battery, comprising the steps of:
s1, uniformly mixing a sodium ion electrolyte, a metal organic frame material and a first polymer in a solvent, then carrying out electrostatic spinning on the surface of an electrode, carrying out ultraviolet irradiation while carrying out electrostatic spinning, and drying to obtain a metal organic frame layer;
s2, dispersing the sodium ion electrolyte into monomers used for synthesizing the second polymer, then adding a cross-linking agent for reaction, and adding the cross-linking agent into the surface of the metal organic framework layer before the monomers used for synthesizing the second polymer are completely reacted, so that the reaction is completed, and the solid electrolyte is used for the sodium ion battery.
In step S1, the volatile solvents in which the first polymer is dissolved are suitable for the present invention.
When the first polymer is polyethylene oxide, the solvent is at least one of dimethylacetamide, N-dimethylformamide, chloroform, tetrahydrofuran, water, methanol, ethanol, propanol and butanol.
When the first polymer is polyvinyl alcohol, the solvent used is water.
When the first polymer is polyvinylpyrrolidone, the solvent is at least one of dimethylacetamide, N-dimethylformamide, water, chloroform, methanol, ethanol, propanol and butanol
When the first polymer is polyvinylidene fluoride, the solvent used is at least one of dimethylacetamide, N-dimethylformamide or chloroform.
When the first polymer is polyacrylonitrile, the solvent used is at least one of dimethylacetamide, N-dimethylformamide, chloroform or tetrahydrofuran.
When the first polymer is polycaprolactone, the solvent used is at least one of dimethylacetamide, N-dimethylformamide, chloroform, tetrahydrofuran, methanol, ethanol, propanol or butanol.
When the first polymer is polylactic acid, the solvent is at least one of N, N-dimethylformamide, chloroform and tetrahydrofuran.
When the first polymer is polyethersulfone, the solvent used is at least one of dimethylacetamide, N-dimethylformamide or chloroform.
When the first polymer is polyurethane, the solvent is at least one of dimethylacetamide, N-dimethylformamide, tetrahydrofuran, water, methanol, ethanol, propanol and butanol.
When the first polymer is polystyrene, the solvent used is at least one of dimethylacetamide, N-dimethylformamide, chloroform or tetrahydrofuran.
In some embodiments, the polymer electrolyte layer includes at least one of a polypropylene ether, a polydimethylsiloxane, a polyvinyl alcohol, a polyethylene oxide, or a polyvinylidene fluoride.
In step S2 of the above method for preparing a solid electrolyte, a catalyst may be added to promote the reaction, and the catalyst may be any material capable of promoting the reaction.
Illustratively, when the polymer electrolyte layer is a polypropylene ether, the monomer used is a propylene ether; the catalyst is a base catalyst and can be at least one selected from sodium hydroxide or potassium hydroxide; the solvent is at least one selected from toluene and dimethyl sulfoxide. The reaction temperature is 20-60 ℃ and the reaction time is 5-50 h.
Illustratively, when the polymer electrolyte layer is polydimethylsiloxane, the monomer used is dimethylsiloxane; the catalyst used may be at least one selected from a base catalyst or an acid catalyst, wherein the base catalyst may be at least one selected from sodium hydroxide or potassium hydroxide, and the acid catalyst may be at least one selected from sulfuric acid or platinic chloride. The reaction temperature is 20-100 ℃, and the reaction time is 5-50 h.
Illustratively, when the polymer electrolyte layer is polyvinyl alcohol, the monomer used is vinyl alcohol, the catalyst used may be at least one selected from ammonium persulfate or potassium persulfate, and the solvent used may be at least one selected from methanol or ethanol. The reaction temperature is 20-100 ℃, and the reaction time is 5-50 h.
Illustratively, when the polymer electrolyte layer is polyethylene oxide, the monomer used is ethylene oxide, the catalyst used is at least one of sodium hydroxide or potassium hydroxide, and the solvent used may be at least one selected from methanol or ethanol. The reaction temperature is 20-100 ℃, and the reaction time is 5-50 h.
Illustratively, when the polymer electrolyte layer is polyvinylidene fluoride, the monomer used is vinylidene fluoride and the catalyst used is a radical initiator. The reaction temperature is 20-100 ℃, the reaction time is 5-50 h, and the reaction is carried out in a gas phase or a liquid phase, wherein the liquid phase can be liquid ammonia.
Example 1
The embodiment provides a solid electrolyte for a sodium ion battery, which comprises a metal organic frame layer, a transition layer and a polymer electrolyte layer which are sequentially formed on the surface of an electrode. Wherein, the raw materials of the metal organic framework layer comprise NaPF6, MIL-88A and polyacrylonitrile, the raw materials of the polymer electrolyte layer comprise NaPF6, stannous chloride and propylene ether, and the metal organic framework layer and the polymer electrolyte layer mutually permeate to form a transition layer.
The embodiment also provides a preparation method of the solid electrolyte for the sodium ion battery, which comprises the following steps:
(1) 1g MIL-88A and 10mmol NaFP 6 Respectively dispersing in 10g of N, N-dimethylformamide, mixing, vigorously stirring at 1000r/min for 3h, then adding 1.2g of polyacrylonitrile, and continuously stirring for 10h to form a viscous solution. The viscous solution was charged into a 20mL syringe equipped with a 21 gauge steel needle for electrospinning for 120min, and spun collection was performed using an aluminum foil coated with a hard carbon negative electrode as a substrate. The diameter of the electrostatic spinning filament is 300-500 nm, the voltage is 22kV, the scanning speed is 20mm/s, the injection speed is 15 mu L/min, the collecting distance is 10cm, and the rotating speed is 500r/min. While electrospinning, ultraviolet irradiation with wavelength of 100nm and irradiation intensity of 1.0mW/cm was performed 2 And forming photoetching holes on the surface of the spinning fiber. Finally, drying in a vacuum drying oven at 80 ℃ to obtain the metal organic framework layer attached to the surface of the aluminum foil coated with the hard carbon negative electrode.
(2) NaFP 6 Dispersing into toluene solution containing propylene ether to form NaFP 6 Adding stannous chloride with the mass concentration of 3% into the mixed solution with the concentration of 1mol/L, adding sodium hydroxide as a catalyst, and carrying out temperature control at 70 DEG CAnd (3) reacting for 3 hours to obtain a reaction liquid which is not completely polymerized.
(3) And (3) adding 0.3mL of the incompletely polymerized reaction solution prepared in the step (2) to the surface of the metal organic framework layer prepared in the step (1), and reacting for 15h at 70 ℃ to obtain the solid electrolyte of the sodium ion battery.
The thickness of the metal organic frame layer of the solid electrolyte for sodium ion battery prepared in this example was 10 μm, the thickness of the transition layer was 8 μm, and the thickness of the polymer electrolyte layer was 10 μm.
Example 2
The embodiment provides a solid electrolyte for a sodium ion battery, which comprises a metal organic frame layer, a transition layer and a polymer electrolyte layer which are sequentially formed on the surface of an electrode. Wherein, the raw materials of the metal organic framework layer comprise sodium tetrafluoroborate, PCN-224 and polyvinylidene fluoride, the raw materials of the polymer electrolyte layer comprise sodium tetrafluoroborate, dimethyl siloxane and epoxy resin, and the metal organic framework layer and the polymer electrolyte layer mutually permeate to form a transition layer.
The embodiment also provides a preparation method of the solid electrolyte for the sodium ion battery, which comprises the following steps:
(1) 0.9g of PCN-224 and 9mmol of sodium tetrafluoroborate were dispersed in 10g of chloroform, respectively, and then mixed, vigorously stirred at 800r/min for 2.5 hours, then 1.0g of polyvinylidene fluoride was added, and stirring was continued for 9.5 hours to form a viscous solution. The viscous solution was charged into a 20mL syringe equipped with a 21 gauge steel needle and electrospun for 80min, and Na-coated was used 3 V 2 (PO 4 ) 3 And taking 10cm x 10cm aluminum foil of the positive electrode as a matrix for spinning collection. The diameter of the electrostatic spinning filament is 0.3mm, the voltage is 18kV, the scanning speed is 10mm/s, the injection speed is 5 mu L/min, the collecting distance is 6cm, and the rotating speed is 300r/min. While electrospinning, ultraviolet irradiation with wavelength of 20nm and irradiation intensity of 0.1mW/cm was performed 2 And forming photoetching holes on the surface of the spinning fiber. Finally, drying in a vacuum drying oven at 80 ℃ to obtain the coating film coated with Na 3 V 2 (PO 4 ) 3 Metal of aluminium foil surface of positive electrodeAnd a machine frame layer.
(2) Dispersing sodium tetrafluoroborate into dimethyl siloxane to form a mixed solution with the concentration of 0.9mol/L, then adding epoxy resin with the mass concentration of 2.5% of the mixed solution, adding platinic chloride as a catalyst, and reacting for 3 hours at 40 ℃ to obtain a reaction solution which is not completely polymerized.
(3) And (3) adding 0.4mL of the incompletely polymerized reaction solution prepared in the step (2) to the surface of the metal organic framework layer prepared in the step (1), and reacting for 5 hours at 40 ℃ to obtain the solid electrolyte of the sodium ion battery.
The thickness of the metal organic frame layer of the solid electrolyte for sodium ion battery prepared in this example was 5 μm, the thickness of the transition layer was 10 μm, and the thickness of the polymer electrolyte layer was 15 μm.
Example 3
The embodiment provides a solid electrolyte for a sodium ion battery, which comprises a metal organic frame layer, a transition layer and a polymer electrolyte layer which are sequentially formed on the surface of an electrode. Wherein, the raw materials of the metal organic framework layer comprise sodium perchlorate, UIO-66 and polystyrene, the raw materials of the polymer electrolyte layer comprise sodium perchlorate, vinyl alcohol and polyacrylate, and the metal organic framework layer and the polymer electrolyte layer mutually permeate to form a transition layer.
The embodiment also provides a preparation method of the solid electrolyte for the sodium ion battery, which comprises the following steps:
(1) 1.1g of UIO-66 and 11mmol of sodium perchlorate are respectively dispersed in 11g of acetone, then mixed, vigorously stirred at 1200r/min for 3.5h, then 1.2g of polyacrylonitrile is added, and stirring is continued for 10.5h to form a viscous solution. The viscous solution was charged into a 20mL syringe equipped with a 21 gauge steel needle for electrospinning for 135min, and spun collection was performed using 10cm x 10cm aluminum foil coated with a hard carbon negative electrode as a substrate. The diameter of the electrostatic spinning filament is 1.0mm, the voltage is 25kV, the scanning speed is 30mm/s, the injection speed is 30 mu L/min, the collecting distance is 15cm, and the rotating speed is 800r/min. Carrying out ultraviolet irradiation while electrostatic spinning, wherein the wavelength of ultraviolet is 400nm, and the irradiation intensity is 2.0mW/cm 2 And forming photoetching holes on the surface of the spinning fiber. Finally, drying in a vacuum drying oven at 80 ℃ to obtain the metal organic framework layer attached to the surface of the aluminum foil coated with the hard carbon negative electrode.
(2) Dispersing sodium perchlorate into ethanol solution of vinyl alcohol to form a mixed solution with the concentration of sodium perchlorate being 1.1mol/L, then adding polyacrylate with the mass concentration of 3.5% of the mixed solution, adding ammonium persulfate as a catalyst, and reacting for 5 hours at 80 ℃ to obtain a reaction solution which is not completely polymerized.
(3) And (3) adding 0.2mL of the incompletely polymerized reaction solution prepared in the step (2) to the surface of the metal organic framework layer prepared in the step (1), and reacting for 3 hours at 80 ℃ to obtain the solid electrolyte of the sodium ion battery.
The thickness of the metal organic frame layer of the solid electrolyte for sodium ion battery prepared in this example was 15 μm, the thickness of the transition layer was 5 μm, and the thickness of the polymer electrolyte layer was 5 μm.
Comparative example 1
The present comparative example provides a solid state electrolyte for a sodium ion battery comprising a metal organic frame layer formed on the surface of an electrode, the metal organic frame layer consisting of NaPF6, MILs-88A and polyacrylonitrile.
The preparation method of the above solid electrolyte for sodium ion battery provided in this comparative example was referred to step (2) in example 1, except that the electrospinning time was 360min. Other operations are the same as those in step (1) of embodiment 1, and will not be described again.
The solid electrolyte for sodium ion battery prepared in this example was tested to have a thickness of 28 μm.
Comparative example 2
The present comparative example provides a solid electrolyte for a sodium ion battery, comprising a polymer electrolyte layer composed of a polypropylene ether and a polyethylene oxide formed on the surface of an electrode.
The preparation method of the solid electrolyte for the sodium ion battery provided by the comparative example comprises the following steps:
(1) NaFP 6 Dispersed to a mass ratio ofIn a mixed solution composed of 1:1 polypropylene ether monomer and ethylene oxide, naFP is formed 6 And adding stannous chloride with the mass concentration of 3% into the mixed solution with the concentration of 1mol/L, and reacting for 3 hours at 70 ℃ to obtain the reaction solution which is not completely polymerized.
(2) And (3) adding 0.5mL of the reaction solution which is prepared in the step (1) and is not completely polymerized to the surface of the aluminum foil coated with the hard carbon negative electrode, and reacting for 15 hours at 70 ℃ to obtain the solid electrolyte for the sodium ion battery.
The thickness of the metal organic frame layer for the solid electrolyte of the sodium ion battery prepared in this example was detected to be 28 μm.
Comparative example 3
The present comparative example provides a solid electrolyte for a sodium ion battery comprising a metal organic frame layer and a polymer electrolyte layer sequentially formed on the surface of an electrode. Wherein the metal organic framework layer is composed of NaPF6, MIL-88A and polyacrylonitrile, and the polymer electrolyte layer is composed of polypropylene ether and polyethylene oxide.
The comparative example also provides a preparation method of the solid electrolyte for the sodium ion battery, which comprises the following steps:
(1) This step is identical to step (1) in embodiment 1 and will not be described again.
(2) NaFP 6 Dispersing into a mixed solution composed of a polypropylene ether monomer and ethylene oxide in a mass ratio of 1:1 to form NaFP 6 And adding stannous chloride with the mass concentration of 3% into the mixed solution with the concentration of 1mol/L, and reacting at 70 ℃ for 18 hours to obtain the completely polymerized polymer.
(3) And (3) adding the completely polymerized polymer prepared in the step (2) into the metal organic frame layer prepared in the step (1) for hot-pressing compounding, so as to be used for the solid electrolyte of the sodium ion battery.
The thickness of the metal organic frame layer for the solid electrolyte of the sodium ion battery prepared in this example was 14 μm and the thickness of the polymer electrolyte layer was 14 μm.
Comparative example 4
The present comparative example provides a solid electrolyte for a sodium ion battery comprising a metal organic frame layer, a transition layer and a polymer electrolyte layer formed in this order on the surface of an electrode. Wherein, metal organic frame layer comprises NaPF6, MIL-88A and polyacrylonitrile, and polymer electrolyte layer comprises polypropylene ether and polyethylene oxide, and metal organic frame layer and polymer electrolyte layer interpenetrate and form the transition layer.
The present comparative example provides the above-mentioned method for preparing a solid electrolyte for a sodium ion battery with reference to example 1, except that in step (1), ultraviolet irradiation is not performed any more while electrospinning. The other steps are the same as those of embodiment 1, and will not be repeated.
The thickness of the metal organic frame layer of the solid electrolyte for sodium ion battery prepared in this example was 10 μm, the thickness of the transition layer was 8 μm, and the thickness of the polymer electrolyte layer was 10 μm.
The solid electrolytes for sodium ion batteries prepared in examples 1 to 3 and comparative examples 1 to 4 were assembled into button solid sodium ion batteries for charge and discharge cycle performance testing, and the assembly steps were as follows: positive electrode shell, spring piece, steel sheet, solid electrolyte @ electrode plate, sodium sheet and negative electrode shell. The plateau capacity and low-temperature capacity decay after 1000 charge-discharge cycles are detailed in table 1. The detection conditions are as follows: all the charge and discharge tests are carried out at the temperature of minus 30 ℃ through a blue electric test system, wherein the charge and discharge voltage range is 1.5-3.8V when the positive electrode is used for charging the battery, the charge and discharge voltage range is 0-3V when the negative electrode is used for charging the battery, and the current density is 50mA/g. As can be seen from the analysis of Table 1, the sodium ion battery prepared by using the solid electrolyte provided by the invention has better ionic conductivity, specific capacity and platform capacity, and better low-temperature-resistant capacity attenuation rate performance.
TABLE 1
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.

Claims (10)

1. A solid electrolyte for a sodium ion battery, comprising a metal organic frame layer, a transition layer and a polymer electrolyte layer formed on the surface of an electrode in this order;
wherein the material of the metal organic framework layer comprises a sodium ion electrolyte, a metal organic framework material and a first polymer;
the metal organic framework layer and the polymer electrolyte layer are mutually penetrated to form the transition layer;
the material of the polymer electrolyte layer includes a sodium ion electrolyte, a crosslinking agent, and a second polymer.
2. The solid state electrolyte for a sodium ion battery of claim 1, wherein the metal organic framework layer is a porous film formed from an irregular stack of nanofibers.
3. The solid state electrolyte for a sodium ion battery of claim 1, wherein the metal organic framework material is at least one of MILs-101, MILs-88A, MIL-88B, UIO-66, PCN-224, MOF-253, or NU-1000; and/or
The first polymer is at least one of polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylidene fluoride, polyacrylonitrile, polycaprolactone, polylactic acid, polyethersulfone, polyurethane or polystyrene.
4. The solid state electrolyte for a sodium ion battery of claim 1, wherein the sodium ion electrolyte is at least one of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, sodium bisoxalato borate, or sodium trifluoromethane sulfonate.
5. The solid state electrolyte for a sodium ion battery of claim 1, wherein the second polymer is at least one of a polypropylene ether, a polydimethylsiloxane, a polyvinyl alcohol, a polyethylene oxide, or a polyvinylidene fluoride; and/or
The cross-linking agent is at least one of glycol stearate, polyacrylate, polyvinyl formate, polyformaldehyde, divinyl phenol, ethyl acrylate formaldehyde condensate, stannous chloride, polyol acrylate, acrylic acid unit, isocyanate, siloxane cross-linking agent, polydimethylsiloxane cross-linking agent, epoxy resin, boric acid or chromic acid.
6. The solid state electrolyte for a sodium ion battery of claim 1, wherein the metal organic frame layer has a thickness of 5 μιη to 15 μιη; and/or
The thickness of the transition layer is 5-10 mu m; and/or
The thickness of the polymer electrolyte layer is 5-15 mu m.
7. A method for preparing the solid electrolyte for a sodium ion battery according to any one of claims 1 to 6, comprising the steps of:
s1, uniformly mixing a sodium ion electrolyte, a metal organic frame material and a first polymer in a solvent, then carrying out electrostatic spinning on the surface of an electrode, carrying out ultraviolet irradiation while carrying out electrostatic spinning, and drying to obtain a metal organic frame layer;
s2, dispersing the sodium ion electrolyte into a second polymer monomer, then adding a cross-linking agent for reaction, and adding the reaction solution to the surface of the metal organic framework layer before the second polymer monomer is completely reacted, so as to completely react, thereby obtaining the solid electrolyte for the sodium ion battery.
8. The method for producing a solid electrolyte for a sodium ion battery according to claim 7, wherein in step S1, the ultraviolet rays have a wavelength of 20nm to 400nm and an irradiation intensity of 0.1mW/cm 2 ~2.0mW/cm 2 。
9. The method for preparing a solid electrolyte for a sodium ion battery according to claim 7, wherein in the step S1, the filament diameter of the electrostatic spinning is 300 nm-500 nm, the voltage is 18 kV-25 kV, the scanning speed is 10 mm/S-30 mm/S, the injection speed is 5 mu L/min-30 mu L/min, the collection distance is 6 cm-15 cm, and the rotating speed is 300 r/min-800 r/min.
10. The method for producing a solid electrolyte for a sodium ion battery according to claim 7, wherein the electrode is a hard carbon anode, a transition metal compound anode, a layered oxide cathode or NaVPO 3 And a positive electrode.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117293382A (en) * 2023-08-30 2023-12-26 齐鲁工业大学(山东省科学院) Na3Zr2Si2PO 12-based solid electrolyte based on metal organic framework bridging and preparation method thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110034330A (en) * 2019-04-10 2019-07-19 华北电力大学 A kind of preparation method of lithium/sode cell composite solid electrolyte
CN110085909A (en) * 2019-05-05 2019-08-02 中南大学 A kind of composite solid electrolyte material and its preparation method and application
CN110911742A (en) * 2019-12-27 2020-03-24 湖北大学 Preparation method of polymer electrolyte composite membrane for solid-state battery
CN112331913A (en) * 2020-12-28 2021-02-05 郑州中科新兴产业技术研究院 Composite solid electrolyte, preparation method and application
CN112490496A (en) * 2020-12-05 2021-03-12 浙江锋锂新能源科技有限公司 Composite solid electrolyte, preparation method thereof and lithium storage battery
CN112968211A (en) * 2021-02-05 2021-06-15 佛山仙湖实验室 Sodium ion solid electrolyte and preparation method and application thereof
CN113921901A (en) * 2021-11-18 2022-01-11 北京化工大学 Metal organic framework based composite nanofiber membrane and preparation method and application thereof
CN115020802A (en) * 2022-05-10 2022-09-06 重庆交通大学绿色航空技术研究院 In-situ ultraviolet light curing nanofiber composite solid electrolyte and preparation method and application thereof
CN115588777A (en) * 2022-10-17 2023-01-10 华中科技大学 Wide-temperature-range solid electrolyte, solid lithium battery and preparation method of solid lithium battery
CN116365018A (en) * 2023-03-17 2023-06-30 武汉理工大学 Metal organic framework reference solid electrolyte and preparation method and application thereof
CN116487681A (en) * 2023-05-12 2023-07-25 湖州南木纳米科技有限公司 Polymer/inorganic composite solid electrolyte membrane and preparation method and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110034330A (en) * 2019-04-10 2019-07-19 华北电力大学 A kind of preparation method of lithium/sode cell composite solid electrolyte
CN110085909A (en) * 2019-05-05 2019-08-02 中南大学 A kind of composite solid electrolyte material and its preparation method and application
CN110911742A (en) * 2019-12-27 2020-03-24 湖北大学 Preparation method of polymer electrolyte composite membrane for solid-state battery
CN112490496A (en) * 2020-12-05 2021-03-12 浙江锋锂新能源科技有限公司 Composite solid electrolyte, preparation method thereof and lithium storage battery
CN112331913A (en) * 2020-12-28 2021-02-05 郑州中科新兴产业技术研究院 Composite solid electrolyte, preparation method and application
CN112968211A (en) * 2021-02-05 2021-06-15 佛山仙湖实验室 Sodium ion solid electrolyte and preparation method and application thereof
CN113921901A (en) * 2021-11-18 2022-01-11 北京化工大学 Metal organic framework based composite nanofiber membrane and preparation method and application thereof
CN115020802A (en) * 2022-05-10 2022-09-06 重庆交通大学绿色航空技术研究院 In-situ ultraviolet light curing nanofiber composite solid electrolyte and preparation method and application thereof
CN115588777A (en) * 2022-10-17 2023-01-10 华中科技大学 Wide-temperature-range solid electrolyte, solid lithium battery and preparation method of solid lithium battery
CN116365018A (en) * 2023-03-17 2023-06-30 武汉理工大学 Metal organic framework reference solid electrolyte and preparation method and application thereof
CN116487681A (en) * 2023-05-12 2023-07-25 湖州南木纳米科技有限公司 Polymer/inorganic composite solid electrolyte membrane and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117293382A (en) * 2023-08-30 2023-12-26 齐鲁工业大学(山东省科学院) Na3Zr2Si2PO 12-based solid electrolyte based on metal organic framework bridging and preparation method thereof

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