CN110690495B - Composite gel polymer solid electrolyte, preparation method thereof and sodium ion battery - Google Patents

Composite gel polymer solid electrolyte, preparation method thereof and sodium ion battery Download PDF

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CN110690495B
CN110690495B CN201910784095.3A CN201910784095A CN110690495B CN 110690495 B CN110690495 B CN 110690495B CN 201910784095 A CN201910784095 A CN 201910784095A CN 110690495 B CN110690495 B CN 110690495B
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贺艳兵
雷丹妮
赵强
郝晓鸽
张丹丰
康飞宇
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Shenzhen Graduate School Tsinghua University
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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
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
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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
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

A preparation method of a composite gel polymer solid electrolyte comprises the following steps: preparing a spinning solution containing aluminum salt, sodium salt and a first high polymer; performing electrostatic spinning on the spinning solution to obtain a precursor film; calcining the precursor film to obtain a fiber film; providing an impregnation liquid comprising a second high molecular polymer; coating the impregnation liquid in the fiber film to obtain a fiber/polymer composite film containing the second high polymer; and placing the fiber/polymer composite film into an organic electrolyte, wherein the organic electrolyte is adsorbed in the fiber/polymer composite film to obtain the composite gel polymer solid electrolyte. The invention also provides a composite gel polymer solid electrolyte and a sodium ion battery.

Description

Composite gel polymer solid electrolyte, preparation method thereof and sodium ion battery
Technical Field
The invention relates to the technical field of energy storage, in particular to a composite gel polymer solid electrolyte, a preparation method thereof and a sodium ion battery.
Background
Sodium ion batteries are receiving more and more attention as substitutes of lithium ion batteries due to the advantages of abundant natural resources, low cost and the like. The sodium metal has the advantages of high theoretical specific capacity (1166mAh/g), low working voltage (-2.71Vvs. SHE) and low cost, and can be used for sodium metal batteries with high working voltage and high energy density, such as sodium-air batteries, sodium-sulfur batteries, sodium-metal halide batteries and the like.
However, there are significant safety issues with the use of sodium metal. Firstly, the current distribution on the surface of the sodium metal is not uniform, so that the deposition and extraction of sodium ions on the surface of the sodium metal cathode are not uniform. Therefore, constructing a uniform and dense solid electrolyte layer on the surface of the sodium metal, effectively passivating the surface of the sodium metal, and inhibiting the formation of sodium dendrites is a challenging task. Secondly, similar to lithium metal, sodium metal and organic liquid electrolyte have very high chemical and electrochemical reactivity, and particularly, side reactions are aggravated at high temperature, and the side reactions lead to continuous decomposition of the electrolyte, so that the sodium metal battery has low coulombic efficiency, poor cycle stability and serious inflation behavior. It follows that these problems must be effectively addressed in order to achieve good cycling stability and safety performance of sodium metal batteries over a wide range of operating temperatures.
Currently, the strategy for stabilizing the sodium metal negative electrode only comprises using an electrolyte stable with sodium metal, constructing a stable artificial protective film on the surface of the sodium metal, and designing a three-dimensional host with a high specific surface area (such as porous copper, nitrogen and sulfur co-doped carbon nanotube paper, three-dimensional carbon felt, graphitized wood, porous aluminum, etc.), thereby inducing uniform deposition of sodium. However, none of these methods can form a stable sodium/electrolyte interface. In addition, the high temperature stability of sodium metal batteries is also of little concern. The above problems greatly hinder the progress of commercial application of sodium metal batteries as well as sodium ion batteries.
Disclosure of Invention
In view of the above, it is desirable to provide a method for preparing a composite gel polymer solid electrolyte having a stable sodium/electrolyte interface, so as to solve the above problems.
In addition, it is necessary to provide the composite gel polymer solid electrolyte.
In addition, it is also necessary to provide a sodium ion battery.
A preparation method of a composite gel polymer solid electrolyte comprises the following steps:
preparing a spinning solution containing aluminum salt, sodium salt and a first high polymer;
performing electrostatic spinning on the spinning solution to obtain a precursor film;
calcining the precursor film to obtain a fiber film;
providing an impregnation liquid comprising a second high molecular polymer;
coating the impregnation liquid in the fiber film to obtain a fiber/polymer composite film containing the second high polymer; and
and placing the fiber/polymer composite film into an organic electrolyte, wherein the organic electrolyte is adsorbed in the fiber/polymer composite film to obtain the composite gel polymer solid electrolyte.
Further, the aluminum salt includes a water-soluble aluminum salt and a high molecular aluminum salt; the water-soluble aluminum salt is at least one of aluminum nitrate and aluminum chloride, and the high-molecular aluminum salt comprises aluminum isopropoxide.
Further, the first high molecular polymer comprises at least one of polyvinylpyrrolidone, polyvinyl alcohol and polyacrylonitrile, and the sodium salt comprises at least one of sodium nitrate, sodium carbonate and sodium chloride.
Further, the spinning solution also comprises nitric acid and glacial acetic acid.
Further, the second high molecular polymer comprises at least one of polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, polyacrylonitrile and polyvinyl chloride.
Further, the thickness of the fiber/polymer composite film is 60-120 μm, and the mass of the second high polymer accounts for 10-25% of the total mass of the fiber/polymer composite film.
The composite gel polymer solid electrolyte comprises a fiber film and a second high molecular polymer loaded on the fiber film to form a fiber/polymer composite film, wherein the gel is a porous structure, and an organic electrolyte is arranged in the porous structure.
Further, the thickness of the fiber/polymer composite film is 60-120 μm, and the mass of the second high polymer accounts for 10-25% of the total mass of the fiber/polymer composite film.
Further, the specific surface area of the fiber film is 3m2/g-6m2The diameter of the fiber in the fiber film is 300nm-500 nm.
A sodium ion battery comprising the composite gel polymer solid state electrolyte.
The preparation method of the composite gel polymer solid electrolyte provided by the invention comprises the steps of preparing a nanofiber-shaped fiber film by an electrostatic spinning technology, forming a polymer with a porous structure in the fiber film by an impregnation method, and adsorbing an organic electrolyte by the polymer to obtain the composite gel polymer solid electrolyte. The composite gel polymer solid electrolyte has a compact and uniform solid-liquid mixed sodium ion conductive path, promotes the rapid conduction of sodium ions in the composite gel polymer solid electrolyte and the uniform transmission and deposition at the interface of the composite gel polymer solid electrolyte/electrode, and thus inhibits the growth of sodium dendrites; the composite gel polymer solid electrolyte has strong adsorption capacity of organic electrolyte, and reduces side reaction of sodium metal and the organic electrolyte; the sodium ion solid-state battery assembled by the composite gel polymer solid-state electrolyte has good electrochemical cycle performance and safety performance in normal temperature and high temperature environments.
Drawings
Fig. 1 is a flow chart of a method for preparing a composite gel polymer solid electrolyte according to an embodiment of the present invention.
FIG. 2A is a SEM image of a fiber film prepared according to an embodiment of the present invention.
FIG. 2B is a SEM image of a cross-section of a fiber film prepared according to an embodiment of the present invention.
Fig. 3A is a scanning electron microscope test chart of the fiber/polymer composite film prepared in the example of the present invention.
FIG. 3B is a SEM image of a cross-section of a fiber/polymer composite film prepared according to an embodiment of the present invention.
Fig. 4 is a test chart of absorption and desorption curves of the fiber film prepared in the embodiment of the invention.
Fig. 5 is a graph showing the cycle stability test of sodium-sodium symmetric cells assembled according to examples of the present invention.
FIG. 6A shows the deposition of 1mAh/cm on a copper sheet for a copper-sodium cell assembled according to an embodiment of the present invention2Scanning electron microscopy test pattern of sodium.
FIG. 6B shows the deposition of 3mAh/cm on a copper sheet for a copper-sodium cell assembled according to an embodiment of the present invention2Scanning electron microscopy test pattern of sodium.
FIG. 7A shows Na assembled according to an embodiment of the present invention3V2(PO4)3[ Na ] Battery, Na3V2(PO4)3Has an areal density of 1mg/cm2And (3) a cycle performance test chart of 1000 cycles at 25 ℃.
FIG. 7B shows Na assembled according to an embodiment of the present invention3V2(PO4)3[ Na ] Battery, Na3V2(PO4)3Has an areal density of 1mg/cm2And cycling performance test chart of 1000 cycles at 60 ℃.
FIG. 7C shows Na assembled according to an embodiment of the present invention3V2(PO4)3[ Na ] Battery, Na3V2(PO4)3Has an areal density of 2.8mg/cm2And (3) a cycle performance test chart of 500 cycles at 25 ℃.
FIG. 8 shows Na assembled according to an embodiment of the present invention3V2(PO4)3Scanning electron microscope test pattern of sodium sheet after 200 times charge and discharge cycle of Na battery.
FIG. 9A shows Na assembled according to an embodiment of the present invention3V2(PO4)3Na after 1000 cycles of Na cell3V2(PO4)3A scanning electron microscope test picture of the section of the/Na battery.
FIG. 9B shows Na after 1000 cycles of the cycle shown in FIG. 9A3V2(PO4)3Element distribution diagram of P element in section of Na battery.
FIG. 9C shows Na after 1000 cycles of the cycle shown in FIG. 9A3V2(PO4)3Element distribution diagram of Na element on section of the/Na battery.
FIG. 9D shows Na after 1000 cycles of the cycle shown in FIG. 9A3V2(PO4)3Element distribution diagram of F element in section of Na battery.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
So that the manner in which the above recited objects, features and advantages of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. In addition, the embodiments and features of the embodiments of the present application may be combined with each other without conflict. In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention, and the described embodiments are merely a subset of the embodiments of the present invention, rather than a complete embodiment. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes all and any combination of one or more of the associated listed items.
Referring to fig. 1, a method for preparing a composite gel polymer solid electrolyte according to an embodiment of the present invention includes the following steps:
step S1: preparing a spinning solution containing aluminum salt, sodium salt and a first high polymer;
the step S1 specifically includes the following steps: mixing the aluminum salt, the sodium salt, nitric acid and glacial acetic acid in deionized water, and stirring for a preset time to form a sol solution; and adding a first high molecular polymer into the sol solution, and stirring for a preset time to obtain the spinning solution.
The aluminum salt includes a water-soluble aluminum salt and a polymer aluminum salt. The water-soluble aluminum salt is at least one of aluminum nitrate and aluminum chloride, the spinning solution comprises 7-9 mol parts of water-soluble aluminum salt, and the water-soluble aluminum salt is used for providing an aluminum source. The high-molecular aluminum salt comprises aluminum isopropoxide, the spinning solution comprises 35-45 mol parts of high-molecular aluminum salt, the high-molecular aluminum salt is used for providing an aluminum source, and meanwhile, the high-molecular aluminum salt is hydrolyzed to increase the viscosity of the spinning solution.
The sodium salt comprises at least one of sodium nitrate, sodium carbonate and sodium chloride, and the spinning solution comprises 8-10 molar parts of sodium salt, and the sodium salt is used for providing a sodium source.
The spinning solution comprises 3.5-5.9 molar parts of the first high polymer, and the first high polymer comprises at least one of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and Polyacrylonitrile (PAN). The first high molecular polymer serves to increase the viscosity of the spinning solution. It is understood that the content of the first high molecular polymer can be adjusted according to the content of the aluminum isopropoxide, so as to prepare a spinning solution with proper viscosity.
The nitric acid and the glacial acetic acid are used for adjusting the pH value, promoting the macromolecule aluminum salt to be hydrolyzed to form stable and transparent sol, increasing the viscosity of the spinning solution, reducing the content of the first macromolecule polymer and improving the density of the nanowires in the finally formed fiber film.
Further, the spinning solution further comprises a lithium salt, wherein the lithium salt comprises at least one of lithium nitrate, lithium carbonate and lithium chloride, and the lithium salt is used for doping lithium ions in the finally formed fiber film.
Step S2: performing electrostatic spinning on the spinning solution to obtain a precursor film;
specifically, the spinning solution is transferred into a needle cylinder, the needle cylinder is placed in a spinning machine, 16kV-20kV voltage is applied to a needle head to carry out electrostatic spinning, the flow rate of the spinning solution is 0.8mL/h-1.2mL/h, the spinning solution is sprayed on a collector in a nanofiber shape, and finally a film is formed, so that the precursor film is obtained.
Step S3: calcining the precursor film to obtain a fiber film;
specifically, the precursor film is placed in a vacuum drying oven for drying for a preset time, and then is placed in a tube furnace for calcination in an air atmosphere. Wherein the calcination specifically comprises heating to 600 ℃ at a heating rate of 5 ℃/min for 1h, and then continuing to heat to 1250 ℃ at a heating rate of 5 ℃/min to obtain the fiber film.
The fiber film comprises beta-Al2O3(NaAl11O17) And beta' -Al2O3(NaAl5O8) A mixture of (a).
During calcination, beta' -Al2O3Is easily converted into beta-Al2O3And beta' -Al2O3Theoretical ionic conductivity ratio of (B-Al)2O3Therefore, the lithium salt is added into the spinning solution to be beneficial to stabilizing beta' -Al2O3Structure of (1), beta' -Al2O3Is more.
Step S4: preparing an impregnation liquid, wherein the impregnation liquid comprises an organic solvent and a second high molecular polymer dissolved in the organic solvent;
the organic solvent includes at least one of acetone, ethanol, acetonitrile, and N, N-dimethylformamide.
The second high molecular polymer includes at least one of polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polymethyl methacrylate (PMMA), polyethylene oxide (PEO), Polyacrylonitrile (PAN), and polyvinyl chloride (PVC).
Step S5: coating the impregnation liquid on the fiber film and drying to obtain a fiber/polymer composite film containing the second high polymer;
after the fiber film coated with the impregnation liquid is dried, the organic solvent is volatilized, and the second high molecular polymer remains in the fibers of the fiber film and forms a porous structure.
The thickness of the fiber/polymer composite film is 60-120 mu m, and the mass of the second high polymer accounts for 10-25% of the total mass of the fiber/polymer composite film.
Step S6: and placing the fiber/polymer composite film into an organic electrolyte, wherein the organic electrolyte is adsorbed in the fiber/polymer composite film to obtain the composite gel polymer solid electrolyte.
The organic electrolyte is a conventional sodium ion battery electrolyte, such as 1M NaClO4Dissolved in ethylene carbonate/diethyl carbonate (EC/DEC) and 5% fluoroethylene carbonate (FEC) was added.
And the organic electrolyte is adsorbed in the fiber/polymer composite film through the porous structure to form the composite gel polymer solid electrolyte.
The fiber/polymer composite film has good adsorption performance, the liquid absorption rate eta of the fiber/polymer composite film is 250-350%, and the mass of the fiber/polymer composite film before the fiber/polymer composite film adsorbs the organic electrolyte is W0The mass of the fiber/polymer composite film after adsorbing the organic electrolyte is WtThe liquid absorption rate eta of the fiber/polymer composite film is as follows:
Figure BDA0002177460950000081
the embodiment of the invention also provides a composite gel polymer solid electrolyte, which comprises the fiber film and a polymer loaded on the fiber film to form the fiber/polymer composite film, wherein the polymer is the second high molecular polymer, the gel is a porous structure, and the porous structure is provided with an organic electrolyte.
The specific surface area of the fiber film is 3m2/g-6m2The diameter of the fiber in the fiber film is 300nm-500 nm.
The invention also provides a sodium ion battery, which comprises a positive electrode, a negative electrode and the composite gel polymer solid electrolyte, wherein the composite gel polymer solid electrolyte is arranged between the positive electrode and the negative electrode.
The present invention will be described below with reference to specific examples.
Dissolving 8mmol of aluminum nitrate, 1.4mmol of lithium nitrate and 9mmol of sodium nitrate in 9.2mL of deionized water, then adding 2.9mL of nitric acid, 1.9mL of glacial acetic acid and 40mmol of aluminum isopropoxide, and stirring for 24 hours to obtain the transparent stable sol solution; then 0.36g of polyvinylpyrrolidone is added, and the mixture is stirred for 12 hours to obtain the spinning solution.
And transferring the spinning solution into a needle cylinder, placing the needle cylinder into a spinning machine for electrostatic spinning, setting the voltage of the electrostatic spinning to be 18kV, setting the flow rate of the spinning solution to be 1mL/h, obtaining the precursor film after the electrostatic spinning is finished, placing the precursor film into a vacuum drying oven for drying for 12h, placing the precursor film into a muffle furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, and then continuing heating to 1250 ℃ at the heating rate of 5 ℃/min to obtain the fiber film.
0.75g of a polyvinylidene fluoride-hexafluoropropylene copolymer was dissolved in 13.5g of acetone and 0.75g of ethanol, and stirred at 50 ℃ for 2 hours. And (3) coating the solution on a fiber film by a dipping method, then naturally airing, and then putting the fiber film into a vacuum oven for drying for 12 hours to obtain the fiber/polymer composite film.
The fiber/polymer composite film is placed in an organic electrolyte (1 MNaClO)4Dissolving in EC/DEC, adding 5% FEC) for 12h to obtain the composite gel polymer solid electrolyte, wherein the organic electrolyte comprises 1M NaClO4The dissolution was in EC/DEC and 5% FEC was added.
The thickness of the fiber/polymer composite film is 80 mu m, and the specific surface area is 2.36m2(ii) in terms of/g. The mass of polyvinylidene fluoride-hexafluoropropylene in the fiber/polymer composite film accounts for 17% of the total mass of the fiber/polymer composite film. The nanowires in the fiber/polymer composite film and the polyvinylidene fluoride-hexafluoropropylene form strong interaction.
Scanning Electron Microscope (SEM) tests were performed on the fiber thin film and the fiber/polymer composite thin film prepared in the examples, and the test results are shown in fig. 2A, 2B, 3A, and 3B. As can be seen from FIGS. 2A and 2B, the fiber film is composed of uniform fibers with a diameter of 300nm-500 nm. As can be seen from fig. 3A and 3B, when the polymer is loaded on the fiber film, the diameter of the fiber loaded with the polymer is significantly increased compared to that before the loading.
In this example, the mass of the fiber/polymer composite film before adsorbing the organic electrolyte was 11.5mg, the mass of the fiber/polymer composite film after adsorbing the organic electrolyte was 55.5mg, and the liquid absorption η of the fiber/polymer composite film was 339.5%.
Referring to fig. 4, the specific surface area of the fiber film prepared in example was measured, fig. 4 is a graph showing the adsorption and desorption curves of the fiber film, and the specific surface area of the fiber film prepared in example was 3.73m2/g。
Sodium sheets are respectively used as a positive electrode and a negative electrode, and the sodium sheets and the composite gel polymer solid electrolyte prepared in the embodiment are assembled into a sodium-sodium symmetrical battery. The electrochemical performance of the symmetric cells was tested, see FIG. 5, at 0.5mA/cm2The current density still circulates stably after circulating for 300h, and the short circuit phenomenon does not occur.
Ion conductivity calculation formula:
Figure BDA0002177460950000101
where σ is the ionic conductivity, L is the thickness of the electrolyte membrane composite gel polymer solid electrolyte, and R is the impedance of the composite gel polymer solid electrolyte, and in this example, L is 80 μm, and S is 2cm2R is 5.6 Ω, and the ion conductivity σ is calculated to be 7.13 × 10-4S/cm。
Copper sheets and sodium sheets are respectively used as a positive electrode and a negative electrode, the copper-sodium batteries are assembled with the composite gel polymer solid electrolyte prepared in the embodiment, and the copper sheets in the two copper-sodium batteries are respectively deposited with 1mAh/cm2And 3mAh/cm2To deposit sodiumThe copper sheet was subjected to scanning electron microscopy testing. Referring to FIG. 6A and FIG. 6B, FIG. 6A and FIG. 6B show the deposition of 1mAh/cm2And 3mAh/cm2The test picture of the sodium scanning electron microscope shows that the surface of the copper sheet after the sodium deposition is even and smooth, and no sodium dendrite is generated, because the composite gel polymer solid electrolyte forms a solid-liquid mixed sodium ion transmission path, the rapid and even conduction of sodium ions in the electrolyte and at the interface of an electrode/electrolyte is promoted, and the growth of the sodium dendrite is obviously inhibited.
Referring to FIG. 7A, FIG. 7B and FIG. 7C, a sodium sheet is used as the negative electrode, Na3V2(PO4)3Is used as a positive electrode and is assembled into Na with the composite gel polymer solid electrolyte prepared in the embodiment3V2(PO4)3a/Na cell, testing said Na3V2(PO4)3Electrochemical performance of the/Na cell. Wherein, the Na3V2(PO4)3Has an areal density of 1mg/cm2Testing of Na at a current density of 1C at 25 ℃ and 60 ℃ respectively3V2(PO4)3The cycling performance of the/Na cell, with a cycle number of 1000, was 95.3% (FIG. 7A) and 78.8% (FIG. 7B) after 1000 cycles at 25 ℃ and 60 ℃ respectively, indicating that Na3V2(PO4)3The Na battery can keep good cycle performance under the environment of normal temperature and high temperature; in another electrochemical cycling performance test, the Na3V2(PO4)3Has an areal density of 2.8mg/cm2The capacity retention reached 95.2% after 500 cycles at a current density of 1C (fig. 7C).
Please refer to table 1, which is Na3V2(PO4)3And the conditions and test results of the/Na battery cycle test.
TABLE 1 Na3V2(PO4)3Perna cell cycling test
Figure BDA0002177460950000111
Please refer to fig. 8, in Na3V2(PO4)3After the Na battery is cycled for 200 times, the sodium sheet is tested by a scanning electron microscope, and the surface of the sodium sheet is still flat without sodium dendrite.
Please refer to fig. 9A, in Na3V2(PO4)3After 1000 times of circulation of the/Na battery, the Na is added3V2(PO4)3The cross section of the/Na cell is tested by scanning electron microscope, please refer to FIG. 9B, FIG. 9C and FIG. 9D, for Na shown in FIG. 9A3V2(PO4)3The energy spectrum test of P element, Na element and F element is carried out on the cross section of the/Na battery, and the Na element can be obviously seen3V2(PO4)3Distribution of elements in the/Na battery, which shows that the composite gel polymer solid electrolyte is respectively mixed with Na3V2(PO4)3The positive electrode and the negative electrode of the sodium sheet are in close contact, so that the interface impedance is reduced.
Beta' -Al in composite gel polymer solid electrolyte during battery cycling2O3Has very strong adsorption capacity to EC and DEC in electrolyte, beta' -Al2O3The adsorption of EC and DEC reduces the side reaction of sodium metal and organic electrolyte, so that the composite gel polymer solid electrolyte is respectively reacted with Na3V2(PO4)3An interface with close contact is formed between the positive electrode and the sodium negative electrode, so that the polarization of the battery is reduced, the growth of sodium dendrite is inhibited, and the Na content is greatly improved3V2(PO4)3Cycling stability of the/Na cell.
The nano-fiber in the fiber film provides a transmission path for sodium ions, and the inorganic conductive network and the second high polymer (gel) are combined to form a compact and uniform solid-liquid mixed sodium ion transmission path, so that the uniform deposition of sodium metal is promoted, a stable and flat solid electrolyte interface is formed on the sodium metal cathode, and the side reaction between the sodium metal cathode and the organic electrolyte and the growth of sodium dendrite are successfully inhibited.
The preparation method of the composite gel polymer solid electrolyte provided by the invention comprises the steps of preparing a nanofiber-shaped fiber film by an electrostatic spinning technology, forming a high molecular polymer with a porous structure on the fiber film by an impregnation method, and adsorbing an organic electrolyte by the fiber/polymer composite film to obtain the composite gel polymer solid electrolyte. The composite gel polymer solid electrolyte has a compact and uniform solid-liquid mixed sodium ion conductive path, promotes the rapid conduction of sodium ions in the composite gel polymer solid electrolyte and the uniform transmission and deposition at the interface of the composite gel polymer solid electrolyte/electrode, and thus inhibits the growth of sodium dendrites; the composite gel polymer solid electrolyte has strong adsorption capacity of organic electrolyte, and reduces side reaction of sodium metal and the organic electrolyte; the sodium ion solid-state battery assembled by the composite gel polymer solid-state electrolyte has good electrochemical cycle performance and safety performance in normal temperature and high temperature environments.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.

Claims (10)

1. The preparation method of the composite gel polymer solid electrolyte is characterized by comprising the following steps of:
preparing a spinning solution containing aluminum salt, sodium salt and a first high polymer;
performing electrostatic spinning on the spinning solution to obtain a precursor film;
calcining the precursor film to obtain a fiber film, wherein the calcining step comprises heating to 600 ℃ at a heating rate of 5 ℃/min for 1h, and then continuing to heat to 1250 ℃ at a heating rate of 5 ℃/min;
providing an impregnation liquid comprising a second high molecular polymer;
coating the impregnation liquid in the fiber film to obtain a fiber/polymer composite film containing the second high polymer; and
and placing the fiber/polymer composite film into an organic electrolyte, wherein the organic electrolyte is adsorbed in the fiber/polymer composite film to obtain the composite gel polymer solid electrolyte.
2. The method of claim 1, wherein the aluminum salt comprises a water-soluble aluminum salt and a polymeric aluminum salt; the water-soluble aluminum salt is at least one of aluminum nitrate and aluminum chloride, and the high-molecular aluminum salt comprises aluminum isopropoxide.
3. The method of claim 1, wherein the first high molecular polymer comprises at least one of polyvinylpyrrolidone, polyvinyl alcohol, and polyacrylonitrile, and the sodium salt comprises at least one of sodium nitrate, sodium carbonate, and sodium chloride.
4. The method of claim 1, wherein the spinning solution further comprises nitric acid and glacial acetic acid.
5. The method of claim 1, wherein the second polymer comprises at least one of polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, polyacrylonitrile, and polyvinyl chloride.
6. The method for preparing the composite gel polymer solid electrolyte according to claim 1, wherein the thickness of the fiber/polymer composite film is 60 μm to 120 μm, and the mass of the second high molecular polymer accounts for 10% to 25% of the total mass of the fiber/polymer composite film.
7. A composite gel polymer solid-state electrolyte prepared by the preparation method of the composite gel polymer solid-state electrolyte according to any one of claims 1 to 6, wherein the composite gel polymer solid-state electrolyte comprises a fiber film and a second high molecular polymer loaded on the fiber film to form a fiber/polymer composite film, the gel is a porous structure, and the organic electrolyte is contained in the porous structure.
8. The composite gel polymer solid electrolyte of claim 7, wherein the thickness of the fiber/polymer composite film is 60 μm to 120 μm, and the mass of the second high molecular polymer accounts for 10% to 25% of the total mass of the fiber/polymer composite film.
9. The composite gel polymer solid electrolyte of claim 8, wherein the fiber membrane has a specific surface area of 3m2/g-6m2The diameter of the fiber in the fiber film is 300nm-500 nm.
10. A sodium-ion battery comprising the composite gel polymer solid electrolyte of any one of claims 7 to 9.
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