CN114865072A - Composite gel solid electrolyte with high safety and preparation method thereof - Google Patents

Composite gel solid electrolyte with high safety and preparation method thereof Download PDF

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CN114865072A
CN114865072A CN202210465900.8A CN202210465900A CN114865072A CN 114865072 A CN114865072 A CN 114865072A CN 202210465900 A CN202210465900 A CN 202210465900A CN 114865072 A CN114865072 A CN 114865072A
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electrolyte
naclo
inorganic
liquid
liquid electrolyte
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刘强
申利影
胡楚彦
叶枫
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Harbin Institute of Technology
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Harbin Institute of 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a high-safety composite gel solid electrolyte and a preparation method thereof, relating to the technical field of solid electrolytes, wherein the high-safety composite gel solid electrolyte comprises an inorganic electrolyte material, an organic gel polymer and a liquid electrolyte; the inorganic electrolyte material has a directional continuous pore structure; the inorganic electrolyte material accounts for 30-70% of the total mass of the inorganic electrolyte material and the organogel polymer. According to the invention, the inorganic electrolyte material is added into the gel solid electrolyte to serve as a supporting framework, and the mass ratio of the inorganic electrolyte material to the organic gel polymer is designed, so that the overall mechanical strength is improved, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane, the circulation stability and the use safety of the sodium ion battery are improved, and meanwhile, the high-safety composite gel solid electrolyte has a directional continuous structure, and the ion transmission path and the ion transmission rate are ensured.

Description

Composite gel solid electrolyte with high safety and preparation method thereof
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a composite gel solid electrolyte with high safety and a preparation method thereof.
Background
As the application of secondary batteries is more and more extensive, the safety problems of batteries in use, such as mobile phone explosion, electric vehicle ignition and the like, also get attention, and therefore, how to ensure the safety of batteries in use is one of the biggest problems faced by battery technology today. At present, replacing the traditional organic liquid electrolyte with solid electrolyte is a measure to solve the safety problem of the battery. Compared with the traditional organic liquid electrolyte, the solid electrolyte is not flammable at high temperature, has low cost, and is not influenced by extreme environment and long-term storage, so the safety performance of the battery can be improved to a certain extent. Common solid electrolytes include inorganic solid electrolytes, organic solid electrolytes (including gel solid electrolytes), and composite solid electrolytes. The gel polymer electrolyte of the sodium ion battery is widely applied to the battery technology due to high ionic conductivity and good flexibility, but most of gel solid electrolytes of the sodium ion battery have low mechanical strength, which easily causes the generated sodium metal dendrite to pierce an electrolyte membrane to cause short circuit or failure of the battery, and influences the cycle stability, rate capability and safety problem in the use process of the battery. Therefore, practical application of the gel solid electrolyte in a sodium ion battery is greatly limited.
Disclosure of Invention
The invention solves the problem of how to improve the problem that the safety of a solid sodium ion battery is influenced by the low mechanical strength of a gel solid electrolyte of the sodium ion battery.
In order to solve the above problems, the present invention provides a composite gel solid electrolyte with high safety, comprising an inorganic electrolyte material, an organogel polymer and a liquid electrolyte; the inorganic electrolyte material has a directional continuous pore structure; the inorganic electrolyte material accounts for 30-70% of the total mass of the inorganic electrolyte material and the organogel polymer.
Further, the liquid electrolyte includes an electrolyte salt and an electrolyte solvent, and the electrolyte salt includes NaClO 4 、NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; the concentration of the electrolyte salt is 0.5-1 mol/L; the electrolyte solvent includes at least ethylene carbonateOne or more of the esters EC, propylene carbonate PC, butyl carbonate BC, diethyl carbonate DEC, dimethyl carbonate DMC, dimethyl ether DME, tetrahydrofuran THF, triethyl phosphate TEP, fluoroethylene carbonate FEC, diethylene glycol dimethyl ether Diglyme.
Further, the liquid electrolyte comprises 0.5M NaClO 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 (EC + DEC) liquid electrolyte, 0.5M NaPF 6 /Diglyme liquid electrolyte, 0.7M NaClO 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC, 0.7M NaPF 6 Diglyme liquid electrolyte, 1M NaClO 4 EC liquid electrolyte, 1M NaClO 4 DEC liquid electrolyte, 1M NaClO 4 Liquid electrolyte of/PC, 1M NaClO 4 (EC + PC) liquid electrolyte, 1M NaPF 6 One of/Diglyme liquid electrolytes; wherein the volume ratio of said EC to said DEC in said EC + DEC is 1: 1; the volume ratio of the EC to the PC in the EC + PC is 1: 1.
further, the inorganic electrolyte material includes NASICON type material, Na-beta' -Al 2 O 3 One of the group consisting of sulfide; wherein the NASICON-type material comprises: na (Na) 3+x M y M' 2–y′ Si 3–z P z O 12 (ii) a Wherein M/M' is one of Zr, Ca, Mg, Zn, La, Sc, Ti and Nb; x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 2; z is more than or equal to 0 and less than or equal to 3;
the sulfide includes: na (Na) 3 R a R' b S 4 Wherein R/R' is one or more of P, Sb and As, and a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1.
Further, the organogel polymer comprises one or more of polyethylene oxide PEO, polymethyl methacrylate PMMA, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, polyvinyl alcohol PVA, polyvinyl chloride, polypropylene oxide, polyvinylidene fluoride.
Compared with the prior art, the composite gel solid electrolyte with high safety has the advantages that the inorganic electrolyte material is added into the gel solid electrolyte to serve as a supporting framework, so that the overall mechanical strength is improved, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane, and the cycle stability and the use safety of the sodium ion battery are improved. The structure of the inorganic electrolyte material is designed, so that the inorganic electrolyte material has a directional continuous pore structure, an ion transmission path is ensured, and the ion transmission rate is increased. Meanwhile, the mass ratio of the inorganic electrolyte material to the organic gel polymer is designed, and the high-safety composite gel solid electrolyte with good mechanical property and good conductivity is finally obtained.
A preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: preparing inorganic electrolyte material into water-based inorganic electrolyte slurry, pouring the water-based inorganic electrolyte slurry into a mold, directionally freezing and molding, and then freezing, drying and sintering at high temperature to obtain an inorganic electrolyte framework with a continuous directional pore structure;
step S2: preparing a liquid electrolyte and an organic gel polymer into a mixed solution, immersing the inorganic electrolyte framework into the mixed solution, carrying out vacuum treatment, and naturally standing or adding a gelling agent to obtain the high-safety composite gel solid electrolyte.
Further, in step S1, the preparing the water-based inorganic electrolyte slurry includes:
and mixing the inorganic electrolyte material with deionized water, adding a dispersing agent and a binder, and stirring to obtain the water-based inorganic electrolyte slurry.
Further, the dispersing agent comprises one of sodium polyacrylate PAAS, polyethylene glycol, polyacrylic acid PAA, sodium polymethacrylate PMAA-Na, tetramethylammonium hydroxide TMAH and sodium pyrophosphate; the dispersant accounts for 0.5 to 3 weight percent of the inorganic electrolyte material.
Further, the binder comprises one of carboxymethyl cellulose CMC, polyvinyl alcohol PVA and sodium polyacrylate; the binder accounts for 1-5% of the inorganic electrolyte material by weight.
Further, in step S1, the sintering temperature includes 1000-.
Compared with the prior art, the preparation method of the high-safety composite gel solid electrolyte has the advantages that the inorganic electrolyte material is subjected to freezing forming, freezing drying and high-temperature sintering to prepare the inorganic electrolyte framework, so that the inorganic electrolyte framework forms a continuous directional pore structure, and then the inorganic electrolyte framework, the organic gel polymer and the electrolyte are combined to form the high-safety composite gel solid electrolyte, so that the integral mechanical strength is improved, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane on the premise of ensuring the ion transmission path and the ion transmission rate, and the circulation stability and the use safety of the sodium ion battery are improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite gel solid electrolyte having high safety in an embodiment of the present invention;
FIG. 2 is a skeletal microstructure of an inorganic electrolyte having a continuous oriented pore structure according to an embodiment of the present invention;
FIG. 3 is a microstructure of a composite gel solid electrolyte with high safety in an embodiment of the present invention;
FIG. 4 is a schematic diagram of a conventional inorganic-gel composite electrolyte structure;
fig. 5 is a schematic structural view of a composite gel solid electrolyte with high safety in an embodiment of the present invention.
Description of reference numerals:
1-mixed solution; 2-inorganic electrolyte skeleton.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is noted that the description of the term "some specific embodiments" in the description of the embodiments herein is intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in fig. 2, 3 and 5, an embodiment of the present invention provides a composite gel solid electrolyte with high safety, including an inorganic electrolyte material, an organogel polymer and a liquid electrolyte; the inorganic electrolyte material has a directional continuous pore structure; the mass percentage of the inorganic electrolyte material in the total mass of the inorganic electrolyte material and the organogel polymer is 30-70%.
According to the high-safety composite gel solid electrolyte provided by the embodiment of the invention, the inorganic electrolyte material is added into the gel solid electrolyte to serve as a supporting framework, so that the integral mechanical strength is improved, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane, and the cycle stability and the use safety of the sodium ion battery are improved. Compared with the conventional inorganic-gel composite electrolyte in which a certain amount of inorganic particles are dispersed in the organogel, as shown in fig. 4, although the strength of the gel polymer is increased to some extent, the effect is not significant, and the sodium ion transport path is not effectively reduced. According to the embodiment of the invention, the structure of the inorganic electrolyte material is designed, so that the inorganic electrolyte material has a directional continuous pore structure, an ion transmission path is ensured, and the ion transmission rate is accelerated. Meanwhile, the mass ratio of the inorganic electrolyte material to the organic gel polymer is designed, and the high-safety composite gel solid electrolyte with good mechanical property and good conductivity is finally obtained.
In some specific embodiments, the liquid electrolyte includes an electrolyte salt and an electrolyte solvent, the electrolyte salt including NaClO 4 、NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; the concentration of the electrolyte salt is 0.5-1 mol/L; the electrolyte solvent at least comprisesOne or more of ethylene carbonate EC, propylene carbonate PC, butyl carbonate BC, diethyl carbonate DEC, dimethyl carbonate DMC, dimethyl ether DME, tetrahydrofuran THF, triethyl phosphate TEP, fluoroethylene carbonate FEC, diethylene glycol dimethyl ether Diglyme.
The electrolyte salt in the embodiment adopts sodium salt, and the sodium salt has richer resources compared with lithium salt, and has good electrochemical performance and better safety performance. The electrolyte solvent in the embodiment is widely selected, is suitable to be used as a medium of a battery and a capacitor with high conductivity, and is beneficial to the conduction of sodium ions.
In some specific embodiments, the liquid electrolyte comprises 0.5M NaClO 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 (EC + DEC) liquid electrolyte, 0.5M NaPF 6 /Diglyme liquid electrolyte, 0.7M NaClO 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC, 0.7M NaPF 6 Diglyme liquid electrolyte, 1M NaClO 4 EC liquid electrolyte, 1M NaClO 4 DEC liquid electrolyte, 1M NaClO 4 Liquid electrolyte of/PC, 1M NaClO 4 (EC + PC) liquid electrolyte, 1M NaPF 6 One of/Diglyme liquid electrolytes; wherein, the volume ratio of EC to DEC in EC + DEC is 1: 1; the volume ratio of EC to PC in EC + PC is 1: 1.
in the embodiment, the organic electrolyte is used as an additive to effectively improve the ionic conductivity of the solid electrolyte, and in order to explore the influence of the salt and solvent with different concentrations on the ionic conductivity of the solid electrolyte, the sodium salt concentration, the sodium salt type and the added solvent are compared in the embodiment to optimize the sodium salt and the solvent with optimal concentrations. In this embodiment, the ionic conductivity of the composite gel solid electrolyte in this concentration range is 1 × 10 by optimizing the mixture ratio of the electrolyte salt and the electrolyte solvent -5 S cm -1 -1×10 -2 S·cm -1 And the ionic conductivity can reach 1 x 10 at room temperature (25℃) -3 S·cm -1 The above. When the electrolyte is applied to sodium ion half batteries and full batteries, the electrolyte can show long cycle performance and high rate performance under the condition of the proportion, and the safety of the batteries is greatly improved.
In some specific embodiments, the inorganic electrolyte material comprises a NASICON type material, Na- β "-Al 2 O 3 One of the group consisting of sulfide; wherein the NASICON type material comprises: na (Na) 3+x M y M' 2–y′ Si 3–z P z O 12 (ii) a Wherein M/M' is one of Zr, Ca, Mg, Zn, La, Sc, Ti and Nb; x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 2; z is more than or equal to 0 and less than or equal to 3;
the sulfide includes: na (Na) 3 R a R' b S 4 Wherein R/R' is one or more of P, Sb and As, and a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1.
The inorganic electrolyte material in the embodiment is a NASICON material or a sulfide, which has excellent ion conductivity, stable chemical properties, a wide electrochemical window, and is beneficial to the improvement of ion conductivity of the sodium ion battery and the obtainment of stable chemical properties. In addition, Na 3+x M y M′ 2–y′ Si 3–z P z O 12 Part or all of the elements in the alloy can be replaced by one of Zr, Ca, Mg, Zn, La, Sc, Ti and Nb, and the selection range is wide.
Na-beta "-Al in the present example 2 O 3 The composite material is a fast ion conductor, has the advantages of high ion conductivity, small electron conduction, chemical sinus property, easy forming and the like, is an important solid electrolyte material, and is also used as a key component and a core material of a sodium ion battery.
The sulfide electrolyte in the embodiment has higher ion conductivity rate, which can reach 10 at room temperature, compared with other types of electrolytes -3 S/cm, which is also an ideal solid-state battery electrolyte material.
In some specific embodiments, the organogel polymer comprises one or more of polyethylene oxide PEO, polymethyl methacrylate PMMA, polyvinylidene fluoride PVDF, polyacrylonitrile PAN, polyvinyl alcohol PVA, polyvinyl chloride, polypropylene oxide, polyvinylidene fluoride.
The organogel polymer in the embodiment has wide selection range, is beneficial to the control of production cost and the accurate control of performance, has the characteristics of good film forming property, high film strength, wide electrochemical stability window, difficult decomposition and the like, and improves the safety and the stability of the composite gel solid electrolyte.
Referring to fig. 1, an embodiment of the present invention further provides a method for preparing a composite gel solid electrolyte with high safety, including the following steps:
step S1: preparing inorganic electrolyte material into water-based inorganic electrolyte slurry, pouring the water-based inorganic electrolyte slurry into a mold, directionally freezing and molding, and then freezing, drying and sintering at high temperature to obtain an inorganic electrolyte framework 2 with a continuous directional pore structure;
step S2: preparing a liquid electrolyte and an organic gel polymer into a mixed solution 1, immersing an inorganic electrolyte framework 2 into the mixed solution 1, carrying out vacuum treatment, and naturally standing or adding a gelling agent to obtain the high-safety composite gel solid electrolyte.
According to the preparation method of the high-safety composite gel solid electrolyte provided by the embodiment of the invention, the inorganic electrolyte material is subjected to freezing forming, freezing drying and high-temperature sintering to prepare the inorganic electrolyte framework 2, so that a continuous directional pore structure is formed, and then the inorganic electrolyte framework is combined with the organic gel polymer and the electrolyte to form the high-safety composite gel solid electrolyte, so that the integral mechanical strength is improved, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane, and the circulation stability and the use safety of a sodium ion battery are improved on the premise of ensuring the ion transmission path and the ion transmission rate.
In step S1 of this embodiment, the structure and composition of the inorganic electrolyte material are accurately controlled in spatial distribution by the method of freeze molding in a mold, and a continuous oriented pore structure is generated. Compared with other methods, the method is more environment-friendly and safer and has high efficiency.
In step S2 of this embodiment, the inorganic electrolyte skeleton 2 is immersed in the mixed solution 1 prepared by the liquid electrolyte and the organogel polymer, and the mixed solution 1 and the inorganic electrolyte skeleton 2 are fully contacted under vacuum condition, so as to increase the contact interface between the inorganic electrolyte material and the mixed solution 1, and effectively reduce the interface resistance. And then naturally standing or adding a gelling agent to enable the mixed solution 1 in the inorganic electrolyte framework 2 to generate sol-gel transformation, thereby obtaining the high-safety composite gel solid electrolyte.
In some specific embodiments, the preparing the water-based inorganic electrolyte slurry in step S1 includes:
and mixing the inorganic electrolyte material with deionized water, adding a dispersing agent and a binder, and stirring to obtain the water-based inorganic electrolyte slurry.
The inorganic electrolyte material in the embodiment adopts powder with a certain particle size, is mixed with deionized water, and then is mixed and stirred with a dispersant and a binder according to a certain proportion to obtain water-based inorganic electrolyte slurry with uniform dispersion and proper viscosity, thereby providing a stable material base for producing a continuous directional pore structure by freezing forming.
In some specific embodiments, the dispersant comprises one of sodium polyacrylate PAAS, polyethylene glycol, polyacrylic acid PAA, sodium polymethacrylate PMAA-Na, tetramethylammonium hydroxide TMAH, sodium pyrophosphate; the dispersant accounts for 0.5 to 3 weight percent of the inorganic electrolyte material. Therefore, the selection and the content of the dispersing agent are helpful for preventing the inorganic electrolyte material from agglomerating and enhancing the dispersibility, the uniformity and the stability of the water-based inorganic electrolyte slurry.
In some specific embodiments, the binder comprises one of carboxymethyl cellulose CMC, polyvinyl alcohol PVA, sodium polyacrylate; the binder accounts for 1 to 5 weight percent of the inorganic electrolyte material. Therefore, the selection of the binder and the dosage thereof are beneficial to the uniform dispersion of the inorganic electrolyte material and simultaneously improve the film-forming property.
In some embodiments, in step S1, the sintering temperature includes 1000-. Therefore, the continuous oriented pore structure of the inorganic electrolyte material in the preparation process is facilitated, and a powerful channel is provided for the complete immersion of the organogel polymer and the electrolyte.
The present invention is explained in detail by the following specific examples, but the present invention is by no means limited to the examples.
Example 1
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, and stirring for 30min to uniformly mix to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1000 ℃, 1100 ℃ and 1200 ℃ respectively, and naturally cooling to obtain 3D Na with certain strength and a continuous directional pore structure 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.5M 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.5M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.5M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 70 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety, wherein the typical microstructure of the composite gel solid electrolyte is shown in figure 3.
Example 2
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; mixing water-based inorganic electrolyte slurryPouring the materials into a mold, freezing at-50 deg.C, freeze-drying at-50 deg.C in a freeze dryer, calcining at 1000 deg.C, 1100 deg.C and 1200 deg.C, and naturally cooling to obtain 3D Na with continuous directional pore structure 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.5M 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.5M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.5M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 60 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 3
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI and NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1000 ℃, 1100 ℃ and 1200 ℃ respectively, and naturally cooling to obtain 3D Na with certain strength and a continuous directional pore structure 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.5M 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.5M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.5M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 50 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 4
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1000 ℃, 1100 ℃ and 1200 ℃ respectively, and naturally cooling to obtain 3D Na with certain strength and a continuous directional pore structure 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.7M 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.7M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.7M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 70 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 5
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1000 ℃, 1100 ℃ and 1200 ℃ respectively, and naturally cooling to obtain 3D Na with certain strength and a continuous directional pore structure 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is respectively4h, 6h, 8h and 10 h; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.7M 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.7M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.7M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 60 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 6
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, mixing uniformly, and adding 0.05g of componentAdding 0.1g of adhesive PVA into TMAH powder, and stirring for 30min to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1100 ℃ respectively, and naturally cooling to obtain 3D Na with a continuous directional pore structure and certain strength 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 0.7M 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC (1:1), 0.7M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 0.7M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 50 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 7
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1100 ℃ respectively, and naturally cooling to obtain 3D Na with a continuous directional pore structure and certain strength 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 1.0M 4 EC liquid electrolyte, 1.0M NaClO 4 DEC liquid electrolyte, 1.0M NaClO 4 Liquid PC electrolyte, 1.0M NaClO 4 Liquid electrolyte of/EC + DEC (1:1), 1.0M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 1.0M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 70 wt%; putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the high-safety electrolyteThe electrolyte is a solid electrolyte of full composite gel.
Example 8
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1100 ℃ respectively, and naturally cooling to obtain 3D Na with a continuous directional pore structure and certain strength 3 Zr 2 Si 2 PO 12 The typical microstructure of the inorganic electrolyte matrix 2 is shown in fig. 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na having a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; it is composed ofThe medium liquid electrolyte is NaClO containing 1.0M 4 EC liquid electrolyte, 1.0M NaClO 4 DEC liquid electrolyte, 1.0M NaClO 4 Liquid PC electrolyte, 1.0M NaClO 4 Liquid electrolyte of/EC + DEC (1:1), 1.0M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 1.0M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 60 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
Example 9
A composite gel solid electrolyte with high safety and a preparation method thereof comprise the following components: na (Na) 3 Zr 2 Si 2 PO 12 ；PVA；TMAH；PAN；NaClO 4 ；NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; EC. One or more electrolyte solvents with different proportions in PC, BC, DEC, DMC, DME, DEC, THF, TEP, FEC and Diglyme.
The preparation method of the composite gel solid electrolyte with high safety comprises the following steps:
step S1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the electrolyte powder for 10 hours on a ball mill to obtain fine powder, and sieving to obtain inorganic electrolyte material powder with uniform particle size smaller than 5 um; 48.7g of Na 3 Zr 2 Si 2 PO 12 Adding inorganic electrolyte material powder into a beaker filled with 85g of deionized water, uniformly mixing, adding 0.05g of dispersant TMAH, finally adding 0.1g of binder PVA, stirring for 30min, and uniformly mixing to obtain water-based inorganic electrolyte slurry; pouring water-based inorganic electrolyte slurry into a mold, freezing at-50 ℃, freeze-drying at-50 ℃ on a freeze dryer, calcining at 1100 ℃ respectively, and naturally cooling to obtain 3D Na with a continuous directional pore structure and certain strength 3 Zr 2 Si 2 PO 12 Inorganic electrolyte skeleton 2, typical of whichThe microstructure is shown in figure 2. Wherein the high-temperature calcination time is 4h, 6h, 8h and 10h respectively; the temperature rise speed is 5 ℃/min;
step S2: na to have a continuous oriented pore structure 3 Zr 2 Si 2 PO 12 Placing inorganic electrolyte skeleton 2 into PAN and liquid electrolyte, and soaking mixed solution 1 formed by organogel polymer and liquid electrolyte into Na with continuous oriented pore structure under vacuum condition 3 Zr 2 Si 2 PO 12 In the voids of the inorganic electrolyte skeleton 2; wherein the liquid electrolyte is NaClO containing 1.0M 4 EC liquid electrolyte, 1.0M NaClO 4 DEC liquid electrolyte, 1.0M NaClO 4 Liquid PC electrolyte, 1.0M NaClO 4 Liquid electrolyte of/EC + DEC (1:1), 1.0M NaPF 6 A Diglyme liquid electrolyte or a liquid electrolyte containing 1.0M sodium salt; wherein the percentage content of the inorganic electrolyte powder is 50 wt%; and putting the obtained composite gel solid electrolyte into a vacuum oven for naturally cooling to form gel, then carrying out vacuum drying overnight at 50 ℃ for 2-4 days, and then naturally cooling to obtain the composite gel solid electrolyte with high safety.
TABLE 1
Figure BDA0003624081480000161
Figure BDA0003624081480000171
Table 1 shows the different solid phase contents of the above examples and other corresponding composite gel solid electrolyte gel polymer electrolytes with high safety and the ionic conductivity (room temperature) under the electrolyte conditions. Therefore, the high-safety composite gel solid electrolyte gel polymer electrolyte has higher ionic conductivity, the integral mechanical strength can be considered, the formed sodium metal dendrite is prevented from puncturing the electrolyte membrane, and the circulation stability and the use safety of the sodium ion battery are further ensured.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. A composite gel solid electrolyte with high safety is characterized by comprising an inorganic electrolyte material, an organic gel polymer and a liquid electrolyte; the inorganic electrolyte material has a directional continuous pore structure; the inorganic electrolyte material accounts for 30-70% of the total mass of the inorganic electrolyte material and the organogel polymer.
2. The composite gel solid electrolyte with high safety according to claim 1, wherein the liquid electrolyte comprises an electrolyte salt and an electrolyte solvent, and the electrolyte salt comprises NaClO 4 、NaPF 6 、NaBF 4 One or more of NaOTf, NaFSI, NaTFSI; the concentration of the electrolyte salt is 0.5-1 mol/L; the electrolyte solvent at least comprises one or more of ethylene carbonate EC, propylene carbonate PC, butyl carbonate BC, diethyl carbonate DEC, dimethyl carbonate DMC, dimethyl ether DME, tetrahydrofuran THF, triethyl phosphate TEP, fluoroethylene carbonate FEC and diethylene glycol dimethyl ether Diglyme.
3. The composite gel solid electrolyte with high safety according to claim 2, wherein the liquid electrolyte comprises 0.5M NaClO 4 EC liquid electrolyte, 0.5M NaClO 4 DEC liquid electrolyte, 0.5M NaClO 4 0.5M NaClO/PC liquid electrolyte 4 (EC + DEC) liquid electrolyte, 0.5M NaPF 6 /Diglyme liquid electrolyte, 0.7M NaClO 4 EC liquid electrolyte, 0.7M NaClO 4 DEC liquid electrolyte, 0.7M NaClO 4 0.7M NaClO/PC liquid electrolyte 4 Liquid electrolyte of/EC + DEC, 0.7M NaPF 6 /Diglyme liquid electrolyte1M NaClO 4 EC liquid electrolyte, 1M NaClO 4 DEC liquid electrolyte, 1M NaClO 4 Liquid electrolyte of/PC, 1M NaClO 4 (EC + PC) liquid electrolyte, 1M NaPF 6 One of/Diglyme liquid electrolytes; wherein the volume ratio of said EC to said DEC in said EC + DEC is 1: 1; the volume ratio of the EC to the PC in the EC + PC is 1: 1.
4. the composite gel solid electrolyte with high safety according to claim 1, wherein the inorganic electrolyte material comprises NASICON-type material, Na- β ″ -Al 2 O 3 One of the group consisting of sulfide; wherein the NASICON-type material comprises: na (Na) 3+x M y M' 2–y′ Si 3–z P z O 12 (ii) a Wherein M/M' is one of Zr, Ca, Mg, Zn, La, Sc, Ti and Nb; x is more than or equal to 0 and less than or equal to 1; y is more than or equal to 0 and less than or equal to 2; z is more than or equal to 0 and less than or equal to 3;
the sulfide includes: na (Na) 3 R a R' b S 4 Wherein R/R' is one or more of P, Sb and As, and a is more than or equal to 0 and less than or equal to 1; b is more than or equal to 0 and less than or equal to 1.
5. The composite gel solid electrolyte with high safety according to claim 1, wherein the organogel polymer comprises one or more of polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyvinyl chloride, polypropylene oxide, and polyvinylidene.
6. A method for preparing a composite gel solid electrolyte having high safety according to any one of claims 1 to 5, comprising the steps of:
step S1: preparing inorganic electrolyte material into water-based inorganic electrolyte slurry, pouring the water-based inorganic electrolyte slurry into a mold, directionally freezing and molding, and then freezing, drying and sintering at high temperature to obtain an inorganic electrolyte framework with a continuous directional pore structure;
step S2: preparing a liquid electrolyte and an organic gel polymer into a mixed solution, immersing the inorganic electrolyte framework into the mixed solution, carrying out vacuum treatment, and naturally standing or adding a gelling agent to obtain the high-safety composite gel solid electrolyte.
7. The method for preparing a composite gel solid electrolyte with high safety according to claim 6, wherein the preparing of the water-based inorganic electrolyte slurry in step S1 includes:
and mixing the inorganic electrolyte material with deionized water, adding a dispersing agent and a binder, and stirring to obtain the water-based inorganic electrolyte slurry.
8. The method for preparing the composite gel solid electrolyte with high safety according to claim 7, wherein the dispersant comprises one of sodium polyacrylate PAAS, polyethylene glycol, polyacrylic acid PAA, sodium polymethacrylate PMAA-Na, tetramethylammonium hydroxide TMAH, and sodium pyrophosphate; the dispersant accounts for 0.5 to 3 weight percent of the inorganic electrolyte material.
9. The method for preparing a composite gel solid electrolyte with high safety according to claim 7, wherein the binder comprises one of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and sodium polyacrylate; the binder accounts for 1-5% of the inorganic electrolyte material by weight.
10. The method as claimed in claim 6, wherein in step S1, the sintering temperature is 1000 ℃ to 1200 ℃, the holding time is 4-10h, and the temperature rising rate is 5 ℃/min.
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