CN114883638A - High-ionic conductivity composite solid electrolyte, preparation method and application - Google Patents

High-ionic conductivity composite solid electrolyte, preparation method and application Download PDF

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CN114883638A
CN114883638A CN202210467374.9A CN202210467374A CN114883638A CN 114883638 A CN114883638 A CN 114883638A CN 202210467374 A CN202210467374 A CN 202210467374A CN 114883638 A CN114883638 A CN 114883638A
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solid electrolyte
ceramic
composite solid
electrolyte
ion
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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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    • 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
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    • H01M2300/0065—Solid electrolytes
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Abstract

The invention provides a high ionic conductivity composite solid electrolyte, a preparation method and an application, relating to the technical field of solid electrolyte materials, wherein the preparation method comprises the following steps: step S1: adding a ceramic electrolyte material into deionized water, sequentially adding a dispersing agent and a binder, and stirring to obtain ceramic electrolyte slurry; step S2: preparing a ceramic electrolyte film from the ceramic electrolyte slurry by a tape casting method, freezing and forming, and obtaining a ceramic solid electrolyte film with a continuous directional pore structure after freeze drying and high-temperature sintering; step S3: and (3) immersing the ceramic solid electrolyte membrane into an organic polymer solution, and performing vacuum treatment to obtain the high-ion-conductivity composite solid electrolyte. The invention optimizes the contact area of the composite solid electrolyte, reduces the interface resistance, shortens the transmission path of ions and improves the ion conductivity of the solid electrolyte.

Description

High-ionic conductivity composite solid electrolyte, preparation method and application
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to a high-ion-conductivity composite solid electrolyte, a preparation method and application.
Background
In the past, basic scientific research and performance evaluation of sodium ion batteries mostly focus on organic electrolyte systems. However, the volatile and combustible organic solvent in the organic electrolyte has great potential safety hazard in the use process of the battery. Therefore, in order to improve the safety of battery use, research is being directed to a solid electrolyte having high safety. The all-solid-state battery using the solid electrolyte has the characteristics of good thermal stability, high safety, long cycle life, multipurpose geometric shape and wide market application prospect.
Currently, solid electrolytes can generally be classified into three major categories: inorganic Solid Electrolytes (ISEs), Solid Polymer Electrolytes (SPEs), and Composite Polymer Electrolytes (CPEs). Inorganic solid electrolytes for sodium ion batteries generally have high ionic conductivity, good thermal stability, and are effective in inhibiting the growth of metallic negative dendrites. However, these inorganic solid electrolytes are fragile and, due to their high rigidity, often cause a large interface resistance when contacting the solid electrodes (positive/negative electrodes). Solid polymer electrolytes, in turn, generally exhibit good mechanical properties, have elastic characteristics, and can make adequate contact with electrode materials, resulting in lower electrical resistance at the electrode interface. However, the existing solid polymer electrolyte for the sodium ion battery generally has poor sodium ion transport at room temperature, which results in poor electrochemical performance of the battery. Based on the above, by integrating the solid polymer electrolyte and the inorganic solid electrolyte for a sodium ion battery, the optimized organic-inorganic composite electrolyte can utilize the advantages of both. However, in the current organic-inorganic composite electrolyte, generally, an inorganic phase is dispersed in a polymer matrix in a form of ceramic particles, so that the organic phase and the inorganic phase are often in staggered distribution, a large number of contact interfaces exist between the two phases, and a large interface resistance exists, which causes problems of increase of internal resistance and polarization of a battery, and finally, reduction of battery capacity and the like.
Disclosure of Invention
The problem to be solved by the present invention is how to improve the capacity of the battery.
In order to solve the above problems, the present invention provides a method for preparing a high ion conductivity composite solid electrolyte, comprising the steps of:
step S1: adding a ceramic electrolyte material into deionized water, sequentially adding a dispersing agent and a binder, and stirring to obtain ceramic electrolyte slurry;
step S2: preparing the ceramic electrolyte slurry into a ceramic electrolyte film by a tape casting method, freezing and forming, and obtaining a ceramic solid electrolyte film with a continuous directional pore structure after freeze drying and high-temperature sintering;
step S3: and immersing the ceramic solid electrolyte membrane into an organic polymer solution, and performing vacuum treatment to obtain the high-ion-conductivity composite solid electrolyte.
Further, in step S1, the ceramic electrolyte material includes Na 3+x M y M′ 2–y′ Si 3–z P z O 12 Wherein M or 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.
Further, in step S1, the weight ratio of the ceramic electrolyte material, the dispersant and the binder is 100: (0.5-3): (1-5).
Further, the dispersing agent comprises one of sodium polyacrylate, polyethylene glycol, polyacrylic acid, sodium polymethacrylate, tetramethylammonium hydroxide and sodium pyrophosphate.
Further, the binder comprises one of carboxymethyl cellulose, polyvinyl alcohol and sodium polyacrylate.
Further, in step S2, the sintering temperature is 1000-.
Further, in step S3, the vacuum processing includes:
completely immersing the organic polymer solution into the continuous oriented pore structure of the ceramic solid electrolyte membrane under vacuum conditions.
Further, the continuous oriented pore structure includes an oriented crossing structure and an oriented parallel structure.
Compared with the prior art, the preparation method of the high ionic conductivity composite solid electrolyte has the advantages that the ceramic electrolyte slurry is obtained by mixing and stirring the ceramic electrolyte, the dispersant and the binder, so that the subsequently formed ceramic solid electrolyte membrane has higher mechanical strength; and then, the pore structure of the ceramic solid electrolyte membrane is controlled by combining a tape casting molding method and an ice template method to obtain the ceramic solid electrolyte membrane with a continuous directional pore structure, so that the organic polymer solution can be completely immersed into the continuous pore structure, the contact area between the ceramic solid electrolyte membrane and the organic polymer solution in the composite solid electrolyte is optimized, the interface resistance between the ceramic solid electrolyte membrane and the organic polymer solution as well as between the ceramic solid electrolyte membrane and an electrode material is reduced, the transmission path of ions in the composite solid electrolyte is shortened, the transmission of the ions is accelerated, the ion conductivity of the solid electrolyte is improved, and the increase of the battery capacity is further facilitated. Meanwhile, the composite solid electrolyte prepared by the method has high strength and good flexibility.
The invention also provides a high ionic conductivity composite solid electrolyte prepared by the preparation method of the high ionic conductivity composite solid electrolyte.
The advantages of the high ionic conductivity composite solid electrolyte of the present invention over the prior art are the same as the advantages of the preparation method of the high ionic conductivity composite solid electrolyte over the prior art, and are not described herein again.
The application of the high-ion conductivity composite solid electrolyte is used for a solid sodium-ion battery. Compared with the prior art, the solid composite electrolyte material prepared by the invention has higher energy density when being used for a solid sodium-ion battery.
Drawings
FIG. 1 is a flow chart of a method for preparing a high ion conductivity composite solid electrolyte according to an embodiment of the present invention;
FIG. 2 is a diagram of the pore size distribution and the micro-topography of the directional crossing structure parallel to the freezing direction according to an embodiment of the present invention;
FIG. 3 is a graph of pore size distribution and microtopography of the oriented crossing structure perpendicular to the freezing direction according to an embodiment of the present invention;
FIG. 4 is a first view of the pore size distribution and the microstructure of the oriented parallel structure according to an embodiment of the present invention;
FIG. 5 is a second graph of the pore size distribution and the microstructure of the oriented parallel structure according to the embodiment of the present invention;
FIG. 6 is a first schematic view of the microstructure of the high ion conductivity composite solid electrolyte according to an embodiment of the present invention;
fig. 7 is a schematic view of the microstructure of the high ion conductivity composite solid electrolyte according to the embodiment of the present invention.
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.
Referring to fig. 1 to 7, a method for preparing a high ion conductivity composite solid electrolyte according to an embodiment of the present invention includes the following steps:
step S1: adding a ceramic electrolyte material into deionized water, sequentially adding a dispersing agent and a binder, and stirring to obtain ceramic electrolyte slurry;
step S2: preparing a ceramic electrolyte film from the ceramic electrolyte slurry by a tape casting method, freezing and forming, and obtaining a ceramic solid electrolyte film with a continuous directional pore structure after freeze drying and high-temperature sintering;
step S3: and (3) immersing the ceramic solid electrolyte membrane into an organic polymer solution, and performing vacuum treatment to obtain the high-ion-conductivity composite solid electrolyte.
According to the preparation method of the high ionic conductivity composite solid electrolyte, ceramic electrolyte, a dispersing agent and a binder are mixed and stirred to obtain ceramic electrolyte slurry, so that a subsequently formed ceramic solid electrolyte membrane has high mechanical strength; and then, the pore structure of the ceramic solid electrolyte membrane is controlled by combining a tape casting molding method and an ice template method to obtain the ceramic solid electrolyte membrane with a continuous directional pore structure, so that the organic polymer solution can be completely immersed into the continuous pore structure, the contact area between the ceramic solid electrolyte membrane and the organic polymer solution in the composite solid electrolyte is optimized, the interface resistance between the ceramic solid electrolyte membrane and the organic polymer solution as well as between the ceramic solid electrolyte membrane and an electrode material is reduced, the transmission path of ions in the composite solid electrolyte is shortened, the transmission of the ions is accelerated, the ion conductivity of the solid electrolyte is improved, and the increase of the battery capacity is further facilitated. Meanwhile, the composite solid electrolyte prepared by the method has high strength and good flexibility.
In step S1 of this embodiment, the ceramic electrolyte material is ball-milled ceramic powder, the ceramic powder meeting the requirements is added into a container with deionized water after being sieved, and then a dispersant and a binder are added respectively and stirred to be uniformly dispersed, so as to obtain a ceramic electrolyte slurry. The reasonable proportion of the ceramic electrolyte material, the dispersant and the binder is utilized to optimize the performance of the ceramic solid electrolyte membrane obtained subsequently.
In step S2 of this embodiment, a ceramic electrolyte slurry is added to a tape casting machine to form a ceramic electrolyte membrane and then freeze-formed, and then added to a freeze-drying machine to freeze-dry, and then sintered at a high temperature for a certain time at a certain temperature to obtain a ceramic solid electrolyte membrane with a continuous directional pore structure.
In step S3 of this example, as shown in fig. 6 and 7, the ceramic solid electrolyte membrane was immersed in an organic polymer solution, and after the organic polymer solution was brought into sufficient contact with the ceramic solid electrolyte membrane under vacuum conditions, the ceramic solid electrolyte membrane was dried and cooled to obtain a highly ion-conductive composite solid electrolyte. Wherein the dark part is a ceramic phase and the grey part is an organic polymer phase. The vacuum treatment of the embodiment improves the contact area between the organic polymer solution and the ceramic solid electrolyte membrane, and effectively reduces the interface resistance.
In some specific embodiments, in step S1, the ceramic electrolyte material includes Na 3+x M y M′ 2–y′ Si 3–z P z O 12 Wherein M or 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 ceramic electrolyte material in the embodiment is a NASICON material, which has excellent ion conduction characteristics, stable chemical properties, a wider electrochemical window, and is beneficial to the sodium ion battery to improve the ion conductivity and obtain stable chemical properties. In addition, Na 3+x M y M′ 2–y′ Si 3–z P z O 12 Some or all of the elements in the alloy can be replaced by one of Zr, Ca, Mg, Zn, La, Sc, Ti, Nb and other elements.
In some specific embodiments, in step S1, the weight ratio of the ceramic electrolyte material, the dispersant and the binder is 100: (0.5-3): (1-5).
In the embodiment, the weight ratio of the ceramic electrolyte material, the dispersing agent and the binder is reasonably designed, so that the micro-structure forming of the ceramic solid electrolyte membrane is facilitated, and the support is provided for improving the contact area and reducing the interface resistance.
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. Therefore, the material is easy to obtain and has wide selection range.
In some specific embodiments, the binder comprises one of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), sodium polyacrylate.
In some specific embodiments, in step S2, the sintering temperature is 1000-. Thus, high-temperature sintering is carried out according to the ceramic electrolyte material, and the ceramic solid electrolyte membrane with the continuous oriented pore structure with the required strength is obtained by adjusting the sintering temperature, the holding time and the temperature rising speed.
In some specific embodiments, in step S3, the vacuum processing includes:
the organic polymer solution is completely impregnated into the continuous oriented pore structure of the ceramic solid electrolyte membrane under vacuum conditions.
In the embodiment, the gas in the continuous directional pore structure is discharged through vacuum negative pressure, so that the organic polymer solution is fully contacted with the pore wall in the ceramic solid electrolyte membrane, the interface resistance is reduced, and the ionic conductivity is improved.
In some specific embodiments, as shown in fig. 2-5, the continuous oriented pore structure includes an oriented cross structure and an oriented parallel structure. Therefore, the organic polymer solution carries out ion transport in a continuous directional pore structure along a certain path, the transmission path of ions in the composite solid electrolyte is shortened, the ion transmission is accelerated, the ion conductivity of the solid electrolyte is improved, and the ion conductivity can reach 1 × 10 at room temperature (25 ℃) -3 S·cm -1 The above.
According to the preparation method of the high-ionic-conductivity composite solid electrolyte, the ceramic electrolyte, the dispersing agent and the binder are mixed and stirred to obtain ceramic electrolyte slurry, so that a subsequently formed ceramic solid electrolyte membrane has high mechanical strength; and then, the pore structure of the ceramic solid electrolyte membrane is controlled by combining a tape casting molding method and an ice template method to obtain the ceramic solid electrolyte membrane with a continuous directional pore structure, so that the organic polymer solution can be completely immersed into the continuous pore structure, the contact area between the ceramic solid electrolyte membrane and the organic polymer solution in the composite solid electrolyte is optimized, the interface resistance between the ceramic solid electrolyte membrane and the organic polymer solution as well as between the ceramic solid electrolyte membrane and an electrode material is reduced, the transmission path of ions in the composite solid electrolyte is shortened, the transmission of ions is accelerated, and the ion conductivity of the solid electrolyte is improved. Meanwhile, the composite solid electrolyte prepared by the method has high strength and good flexibility.
The embodiment of the invention also provides the high-ion-conductivity composite solid electrolyte prepared by the preparation method.
The advantages of the high ionic conductivity composite solid electrolyte in the embodiment of the invention compared with the prior art are the same as the advantages of the preparation method of the high ionic conductivity composite solid electrolyte compared with the prior art, and are not repeated herein.
The application of the high-ion-conductivity composite solid electrolyte provided by the embodiment of the invention is used for the solid sodium-ion battery, and the solid composite electrolyte material prepared by the embodiment of the invention has higher energy density compared with the solid sodium-ion battery in the prior art.
Example 1
A preparation method of a high ionic conductivity composite solid electrolyte comprises the following components: na (Na) 3 Zr 2 Si 2 PO 12 The preparation method of the high ion conductivity composite solid electrolyte comprises the following steps:
s1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling ceramic electrolyte material in a ball mill for 10h to obtain fine powder, and sieving to obtain 9.732g of Na with uniform particle size 3 Zr 2 Si 2 PO 12 Adding the ceramic electrolyte powder into a beaker filled with 17g of deionized water, uniformly mixing, adding 0.02g of dispersant TMAH, finally adding 0.03g of binder PVA, and stirring for about 30min to uniformly mix to obtain ceramic electrolyte slurry;
s2: pouring the ceramic electrolyte slurry into a tape casting forming machine, preparing a ceramic electrolyte film with the thickness of 0.4mm by tape casting forming, and freezing at the temperature of minus 50 ℃; and (3) placing the frozen and molded solid ceramic electrolyte membrane on a freeze dryer, carrying out freeze drying at-50 ℃, calcining at 1100 ℃, and naturally cooling to obtain the ceramic solid electrolyte membrane with a continuous oriented pore structure. Wherein the high-temperature calcination time is respectively 3h, 5h, 7h, 9h and 11h, and the temperature rise speed is 5 ℃/min;
s3: and putting the obtained ceramic solid electrolyte membrane with the continuous oriented pore structure into a PEO solution, completely immersing the ceramic solid electrolyte membrane into gaps of the ceramic solid electrolyte membrane with the continuous oriented pore structure under a vacuum condition, putting the ceramic solid electrolyte membrane into a vacuum oven for overnight drying at 60 ℃, and naturally cooling to obtain the high-ion-conductivity composite solid electrolyte.
Example 2
A preparation method of a high ionic conductivity composite solid electrolyte comprises the following components: na (Na) 3 Zr 2 Si 2 PO 12 The preparation method of the high ion conductivity composite solid electrolyte comprises the following steps:
s1: mixing Na 3 Zr 2 Si 2 PO 12 Ball milling the ceramic electrolyte material in a ball mill for 10h to obtain fine powder, and sieving to obtain uniform 9.732gNa 3 Zr 2 Si 2 PO 12 A ceramic electrolyte powder; adding the ceramic electrolyte powder into a beaker filled with 17g of distilled water, adding 0.01g of dispersant TMAH and 0.02g of binder PVA, and stirring for 30min to uniformly mix the components to obtain ceramic electrolyte slurry;
s2: pouring the ceramic electrolyte slurry into a tape casting forming machine, preparing a ceramic electrolyte film with the thickness of 0.4mm by tape casting forming, and freezing at the temperature of-196 ℃; and (3) placing the frozen and molded solid ceramic electrolyte membrane on a freeze dryer, carrying out freeze drying at-50 ℃, calcining at 1100 ℃, and naturally cooling to obtain the ceramic solid electrolyte membrane with a continuous oriented pore structure. Wherein the high-temperature calcination time is respectively 3h, 5h, 7h, 9h and 11h, and the heating speed is 5 ℃/min;
s3: mixing Na 3 Zr 2 Si 2 PO 12 Placing into PEO solution, and soaking completely under vacuumAnd putting the electrolyte into a gap of a ceramic solid electrolyte membrane with a continuous oriented pore structure, putting the electrolyte into a vacuum oven for overnight drying at 60 ℃, and naturally cooling to obtain the high-ion-conductivity composite solid electrolyte.
Example 3
A preparation method of a high ionic conductivity composite solid electrolyte comprises the following components: na (Na) 3+2x Zr 2- x Ca x Si 2 PO 12 (ii) a Polyethylene oxide PEO; tetramethylammonium hydroxide TMAH; polyvinyl alcohol PVA and the preparation method of the high ion conductivity composite solid electrolyte comprise the following steps:
s1: mixing Na 3+2x Zr 2-x Ca x Si 2 PO 12 Ball-milling the ceramic electrolyte material on a ball mill for 10 hours to obtain fine powder, and sieving the fine powder; wherein, Na 3+2x Zr 2-x Ca x Si 2 PO 12 X in the ceramic electrolyte powder is more than or equal to 0 and less than or equal to 0.3; specifically, x is 0, 0.05, 0.1, 0.15, 0.2, 0.25, and 0.3, respectively; the obtained homogeneous 9.732gNa 3+2x Zr 2-x Ca x Si 2 PO 12 Adding the ceramic electrolyte powder into a beaker filled with 17g of distilled water, adding 0.01g of dispersant TMAH and 0.02g of binder PVA, and stirring for 30min to uniformly mix the components to obtain ceramic electrolyte slurry;
s2: pouring the ceramic electrolyte slurry into a tape casting forming machine, preparing a ceramic electrolyte film with the thickness of 0.4mm by tape casting forming, and freezing at the temperature of-196 ℃; placing the frozen and molded solid ceramic electrolyte membrane on a freeze dryer, carrying out freeze drying at-50 ℃, calcining at 1100 ℃, keeping the temperature for 5h, and carrying out natural cooling at the temperature rise speed of 5 ℃/min to obtain a ceramic solid electrolyte membrane with a continuous directional pore structure;
s3: and putting the obtained ceramic solid electrolyte membrane with the continuous oriented pore structure into a PEO solution, completely immersing the ceramic solid electrolyte membrane into gaps of the ceramic solid electrolyte membrane with the continuous oriented pore structure under a vacuum condition, putting the ceramic solid electrolyte membrane into a vacuum oven for overnight drying at 60 ℃, and naturally cooling to obtain the high-ion-conductivity composite solid electrolyte.
Example 4
A preparation method of a high ionic conductivity composite solid electrolyte comprises the following components: na (Na) 3 Zr 2 Si 2 PO 12 (ii) a PVDF (polyvinylidene fluoride); tetramethylammonium hydroxide TMAH; polyvinyl alcohol PVA and the preparation method of the high ion conductivity composite solid electrolyte comprise the following steps:
s1: mixing Na 3 Zr 2 Si 2 PO 12 The ceramic electrolyte material was ball milled in a ball mill for 10 hours to obtain a fine powder and sieved to obtain uniform 9.732g of Na 3 Zr 2 Si 2 PO 12 Adding the ceramic electrolyte powder into a beaker filled with 17g of distilled water, adding 0.01g of dispersant TMAH and 0.02g of binder PVA, and stirring for 30min to uniformly mix the components to obtain ceramic electrolyte slurry;
s2: pouring the ceramic electrolyte slurry into a tape casting forming machine, preparing a ceramic electrolyte film with the thickness of 0.4mm by tape casting, freezing and forming at the temperature of-196 ℃, putting the frozen and formed solid ceramic electrolyte film on a freeze dryer, carrying out freeze drying at the temperature of-50 ℃, calcining at the temperature of 1100 ℃, keeping the temperature for 5 hours, raising the temperature at the speed of 5 ℃/min, and naturally cooling to obtain the ceramic solid electrolyte film with a continuous directional pore structure;
s3: and putting the obtained ceramic solid electrolyte membrane with the continuous oriented pore structure into a PVDF mixed solution, completely immersing the ceramic solid electrolyte membrane into gaps of the ceramic solid electrolyte membrane with the continuous oriented pore structure under a vacuum condition, putting the ceramic solid electrolyte membrane into a vacuum oven for overnight drying at 60 ℃, and naturally cooling to obtain the high-ion-conductivity composite solid electrolyte.
Example 5
A preparation method of a high ionic conductivity composite solid electrolyte comprises the following components: na (Na) 3 Zr 2 Si 2 PO 12 (ii) a PEO-PVDF; tetramethylammonium hydroxide TMAH; the preparation method of the polyvinyl alcohol PVA and the high ionic conductivity composite solid electrolyte comprises the following steps:
s1: mixing Na 3 Zr 2 Si 2 PO 12 Ball-milling the ceramic electrolyte material on a ball mill for 10 hours to obtain fine powder, sieving the fine powder to obtain 9.732g of uniform ceramic electrolyte powder, adding the powder into a beaker filled with 17g of distilled water, adding 0.01g of dispersant TMAH and 0.02g of binder PVA, stirring the mixture for 30 minutes, and uniformly mixing the mixture to obtain ceramic electrolyte slurry;
s2: pouring the ceramic electrolyte slurry into a tape casting forming machine, preparing a ceramic electrolyte film with the thickness of 0.4mm by tape casting, freezing and forming at the temperature of-196 ℃, putting the frozen and formed solid ceramic electrolyte film on a freeze dryer, carrying out freeze drying at the temperature of-50 ℃, calcining at the temperature of 1100 ℃, keeping the temperature for 5 hours, raising the temperature at the speed of 5 ℃/min, and naturally cooling to obtain the ceramic solid electrolyte film with a continuous directional pore structure;
s3: and putting the obtained ceramic solid electrolyte membrane with the continuous oriented pore structure into a PEO-PVDF mixed solution, completely immersing the ceramic solid electrolyte membrane into gaps of the ceramic solid electrolyte membrane with the continuous oriented pore structure under a vacuum condition, putting the ceramic solid electrolyte membrane into a vacuum oven for overnight drying at 60 ℃, and naturally cooling to obtain the high-ion-conductivity composite solid electrolyte.
TABLE 1
Composite electrolyte material Freezing temperature Calcination time Ionic conductivity (25 ℃ C.)
Na 3 Zr 2 Si 2 PO 12 /PEO -50℃ 5h 7.6x10 -5 Scm -1
Na 3 Zr 2 Si 2 PO 12 /PEO -196℃ 5h 9.2x10 -5 Scm -1
Na 3+2x Zr 2-x Ca x Si 2 PO 12 /PEO -196℃ 5h 3.4x10 -4 Scm -1
Na 3 Zr 2 Si 2 PO 12 /PVDF -196℃ 5h 8.1x10 -5 Scm -1
Na 3 Zr 2 Si 2 PO 12 /PEO-PVDF -196℃ 5h 8.7x10 -5 Scm -1
The data in table 1 are the ionic conductivities of the high ion conductive composite solid electrolytes in the above examples at room temperature.
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 preparation method of a high ionic conductivity composite solid electrolyte is characterized by comprising the following steps:
step S1: adding a ceramic electrolyte material into deionized water, sequentially adding a dispersing agent and a binder, and stirring to obtain ceramic electrolyte slurry;
step S2: preparing the ceramic electrolyte slurry into a ceramic electrolyte film by a tape casting method, freezing and forming, and obtaining a ceramic solid electrolyte film with a continuous directional pore structure after freeze drying and high-temperature sintering;
step S3: and immersing the ceramic solid electrolyte membrane into an organic polymer solution, and performing vacuum treatment to obtain the high-ion-conductivity composite solid electrolyte.
2. The method for producing a high ion-conductive composite solid electrolyte according to claim 1, wherein in step S1, the ceramic electrolyte material includes Na 3+x M y M′ 2–y′ Si 3–z P z O 12 Wherein M or 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.
3. The method for producing a high ion-conductive composite solid electrolyte according to claim 1, wherein in step S1, the weight ratio of the ceramic electrolyte material, the dispersant and the binder is 100: (0.5-3): (1-5).
4. The method of claim 3, wherein the dispersant comprises one of sodium polyacrylate, polyethylene glycol, polyacrylic acid, sodium polymethacrylate, tetramethylammonium hydroxide, and sodium pyrophosphate.
5. The method of preparing a high ion conductive composite solid electrolyte according to claim 3, wherein the binder comprises one of carboxymethyl cellulose, polyvinyl alcohol, and sodium polyacrylate.
6. The method as claimed in claim 1, wherein in step S2, the sintering temperature is 1000-.
7. The method for producing a high ion-conductive composite solid electrolyte according to claim 1, wherein the vacuum treatment comprises, in step S3:
completely immersing the organic polymer solution into the continuous oriented pore structure of the ceramic solid electrolyte membrane under vacuum conditions.
8. The method of producing a high ion conductive composite solid electrolyte according to claim 7, wherein the continuous oriented pore structure includes an oriented cross structure and an oriented parallel structure.
9. A high ion conductive composite solid electrolyte, characterized by being produced by the production method of the high ion conductive composite solid electrolyte according to any one of claims 1 to 8.
10. The use of the high ion conductivity composite solid electrolyte according to claim 9, wherein the high ion conductivity composite solid electrolyte is used in a solid sodium ion battery.
CN202210467374.9A 2022-04-29 2022-04-29 High-ionic conductivity composite solid electrolyte, preparation method and application Pending CN114883638A (en)

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