CN111725562A - Method for preparing oxide type ceramic fabric composite solid electrolyte by taking silk fabric as sacrificial template - Google Patents
Method for preparing oxide type ceramic fabric composite solid electrolyte by taking silk fabric as sacrificial template Download PDFInfo
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Abstract
The invention relates to a preparation method of an energy storage system device material, in particular to a method for preparing an oxide type ceramic fabric composite solid electrolyte by taking a silk fabric as a sacrificial template, and belongs to the technical field of preparation of energy storage system device materials. Firstly, preparing a certain type of oxide type ceramic fabric metal ion precursor solution; then, dipping the cleaned silk fabric into the precursor solution, and calcining at high temperature to obtain an oxide type ceramic fabric; and finally, casting the polymer electrolyte of a polymer-conductive lithium salt system to obtain the oxide type ceramic fabric composite solid electrolyte. The material can be applied to a flexible solid-state lithium battery, and has good electrochemical performance and mechanical flexibility.
Description
Technical Field
The invention relates to a preparation method of an energy storage system device material, in particular to a method for preparing an oxide type ceramic fabric composite solid electrolyte by taking a silk fabric as a sacrificial template, and belongs to the technical field of preparation of energy storage system device materials.
Background
The rapid development of wearable electronic products, electric vehicles and smart grids requires energy storage devices with high energy density, high safety and good mechanical flexibility to be matched with the wearable electronic products. Lithium ion battery cellThe development of decades has become the mainstream energy storage device of the present electronic products. However, the conventional commercial lithium ion battery has graphite as a negative electrode, which has 372 mAh g only-1The theoretical capacity of (2) has a major drawback of low energy density. In addition, the organic liquid electrolyte used in the battery is inflammable and easy to leak, and is very easy to cause serious safety accidents. Meanwhile, the rigid electrode, the current collector and the liquid electrolyte also make the lithium ion battery difficult to realize flexibility, and cannot meet the market demands of flexibility and wearability.
In response to many of the problems of conventional lithium ion batteries, an effective solution is to replace the organic liquid electrolyte with a solid electrolyte. The solid electrolyte is not flammable, is stable in air, and is greatly improved in safety compared with a liquid electrolyte. Furthermore, the use of a solid electrolyte allows to have the lowest chemical potential (-3.04V) and the highest theoretical capacity (3860 mAh g)-1) The lithium metal of (2) is directly available as a negative electrode. Solid electrolytes are currently mainly classified into two categories: organic polymer solid electrolytes and inorganic ceramic solid electrolytes. The polymer solid electrolyte is simple to prepare and excellent in mechanical flexibility, but the polymer solid electrolyte is low in ionic conductivity at room temperature and narrow in electrochemical stability window, and cannot meet the use requirements of batteries. The ceramic solid electrolyte can be subdivided into sulfide type ceramic solid electrolyte and oxide type ceramic solid electrolyte, and the sulfide electrolyte has high lithium ion conductivity (10) at room temperature-2S cm-1) However, it is not stable at room temperature, and it causes inconvenience in mass production and commercial use. The oxide solid electrolyte has high ion conductivity (10) at room temperature-4S cm-1) And is stable in the atmosphere and water. Unfortunately, oxide ceramic solid electrolytes are rigid and fragile, and have high interfacial resistance between electrodes and electrolytes, which cannot meet the requirement of flexibility.
Therefore, combining the advantages of both organic and inorganic solid electrolytes, the preparation of a composite solid electrolyte is an ideal choice. Composite solid electrolytes are typically prepared by dispersing inorganic oxide ceramic nanoparticles in an organic polymer matrix. The ceramic nanoparticle filler increases the ionic conductivity of the solid electrolyte as a whole, while the polymer gives it mechanical flexibility. However, the content of the ceramic nanoparticle filler in the composite solid electrolyte is only 10-20 wt%, because the surface energy of the inorganic ceramic and the organic polymer is greatly different, and the ceramic nanoparticles are easy to agglomerate under the high-concentration ceramic content, which seriously affects the overall ionic conductivity of the composite solid electrolyte. In addition, even at a low concentration of ceramic, since the ceramic nanoparticles are dispersed with each other, a continuous ion transmission path cannot be formed, which seriously affects the ion-conducting effect of the composite solid electrolyte.
Disclosure of Invention
The invention provides an oxide type ceramic fabric composite solid electrolyte material for a solid lithium battery.
The invention also provides a preparation method of the oxide type ceramic fabric composite solid electrolyte material for the solid lithium battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following steps:
(1) preparing an oxide type ceramic solid electrolyte metal ion precursor solution: dissolving metal ion precursor salt containing oxide type ceramic solid electrolyte into a proper amount of acetic acid-absolute ethyl alcohol solution, adding a proper amount of hetero-atom precursor salt as a doping agent, and stirring at room temperature to form a uniform solution;
(2) preparation of oxide type ceramic fabric:
washing undyed silk fabric with deionized water and absolute ethyl alcohol, drying, and removing surface impurities;
soaking the cleaned silk fabric in the precursor solution obtained in the step (1), fully stirring, washing with absolute ethyl alcohol, and drying;
placing the silk fabric soaked with the precursor solution in a tubular furnace, calcining at 600-1000 ℃ for 2-6h in air, naturally cooling, taking out the oxide type ceramic fabric, and placing the oxide type ceramic fabric in a glove box filled with argon for later use;
(3) preparing an organic polymer solid electrolyte solution:
selecting a polymer capable of being used as a solid electrolyte and a conductive lithium salt, and respectively drying the polymer and the conductive lithium salt in vacuum within the temperature range below the respective melting points for later use;
dissolving a polymer and a conductive lithium salt in acetonitrile, and fully stirring at room temperature to form a uniformly mixed organic polymer solid electrolyte solution;
(4) preparing an oxide type ceramic fabric composite solid electrolyte:
sucking the organic polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the solution into a mould;
placing the oxide type ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mould fully paved with a polymer solution, and pouring a layer of organic polymer solid electrolyte solution to form a sandwich structure;
and when the acetonitrile in the organic polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and drying at the temperature of 40-70 ℃ for 12-48h to obtain the oxide type ceramic fabric composite solid electrolyte. The total thickness of the composite solid electrolyte membrane is generally maintained at 100 μm to 150 μm, and the thickness of each layer is difficult to control because of PEO-LiClO4The polymer solid electrolyte solution penetrates into the ceramic fabric and finally forms a whole.
The preparation method is simple, large-scale production can be realized, the obtained oxide type ceramic fabric can keep the tissue structure of the original silk fabric, and a three-dimensional ion guide path is formed. The finally obtained oxide type ceramic fabric composite solid electrolyte has good mechanical flexibility, can be bent and folded, has good electrochemical performance when being used as a solid electrolyte material of an all-solid-state lithium metal battery, and can meet the requirements of a flexible battery.
In response to the problems in the prior art, an effective strategy is to increase the ceramic content in the composite solid electrolyte and maintain a continuous 3D ion transport path. The novel engineering material prepared by the template method has various shapes and structures, is simple to prepare and can be produced in a large scale. Silk, as a natural protein fiber, has high water absorption and excellent mechanical strength. In addition, the amino acid residues in the fibroin molecule have good adsorption properties for metal ions, because-OH and-COOH in the amino acids are easily complexed with metal ions to form coordination compounds. These advantages make silk very suitable as a template for preparing oxide ceramic materials.
In order to realize high ionic conductivity and good mechanical flexibility of the solid electrolyte, the oxide type inorganic ceramic fabric solid electrolyte can be prepared by using silk fabric as a template, and then an organic polymer is compounded to obtain the compound type solid electrolyte. The continuous 3D ion conduction path of the oxide type ceramic fabric can improve the ion conduction effect of the whole solid electrolyte, and the polymer matrix endows the whole with mechanical flexibility. The composite material combining the electrochemical performance and the mechanical flexibility has wide application prospect in solid-state batteries.
Preferably, the metal ion precursor salt in step (1) is selected from precursor salts required for garnet-type, NASICON-type, perovskite-type or anti-perovskite-type ceramics, and the hetero-atomic precursor salt is selected from Al salt, Nb salt or Ta salt.
Preferably, the calcination temperature of the silk fabric impregnated with the precursor solution in the step (2) is 700-900 ℃, and the calcination time is 2-4 h.
Preferably, the polymer in step (3) may be selected from polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC) and the conductive lithium salt may be selected from lithium halide (LiX, X = F, Cl, Br, I), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) And the like.
Preferably, the acetic acid in step (1) is present in an amount of 5 to 25vol.% in anhydrous ethanol.
Preferably, the weave structure of the silk fabric in the step (2) is double-crepe, crepe satin, electric power spinning, doupion, taffeta, twill, georgette or east-wind yarn.
Preferably, the silk fabric is soaked in the precursor solution in the step (2), and then the stirring temperature is 50-70 ℃, and the stirring time is 2-6 h.
Preferably, the stirring time of the polymer and the conductive lithium salt in the step (3) in acetonitrile is 24-48 h.
Preferably, the drying temperature of the composite solid electrolyte membrane in the step (4) is 50 to 60 ℃ and the drying time is 24 to 48 hours.
The oxide type ceramic fabric composite solid electrolyte for the flexible solid lithium battery is prepared by the preparation method.
Firstly, preparing oxide type ceramic fabric metal ion precursor solution with a certain crystal form; then, dipping the cleaned silk fabric into the precursor solution, and calcining at high temperature to obtain an oxide type ceramic fabric; and finally, pouring a polymer electrolyte of a polymer-conductive lithium salt system to obtain the oxide type ceramic fabric composite solid electrolyte, wherein the material can be applied to the field of energy storage of flexible lithium batteries. The method of the invention has the following characteristics:
(1) the preparation method is simple, the reaction conditions are easy to control and realize, and the large-scale production can be realized;
(2) the oxide type ceramic fabric can keep the tissue structure of the original silk fabric template and has a continuous 3D ion guide path;
(3) oxide type ceramic fabrics with different crystal types can be prepared by adjusting the types of the added precursor salts, and in addition, heterogeneous atom precursor salts are added into the precursor salts to obtain heterogeneous atom doped oxide type ceramic fabrics;
(4) the obtained oxide type ceramic fabric composite solid electrolyte can be applied to a lithium battery, and has good electrochemical performance and mechanical flexibility;
(5) the method for preparing the inorganic ceramic by taking the silk base (silkworm cocoon, fiber, yarn, fabric, silk hydrogel and the like) as the template can be expanded to other fields of medical treatment, catalysis, sensing, environment and the like.
Drawings
FIG. 1 is an X-ray electron diffraction (XRD) pattern of the Al-LLZO ceramic fabric obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the Nb-LLZO ceramic fabric prepared in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the Ta-LLZO ceramic fabric produced in example 3;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of a Ta-LLZO ceramic fabric composite solid electrolyte prepared in example 3;
FIG. 5 is an Electrochemical Impedance Spectroscopy (EIS) graph of a stainless steel/solid electrolyte/stainless steel symmetric cell with Ta-LLZO ceramic fabric composite solid electrolyte made in example 4;
FIG. 6 is a graph of the cycle performance of a Li/solid electrolyte/Li symmetrical battery of Ta-LLZO ceramic fabric composite solid electrolyte obtained in example 4;
FIG. 7 is an Electrochemical Impedance Spectroscopy (EIS) chart of a stainless steel/solid electrolyte/stainless steel symmetric cell of LLTO ceramic fabric composite solid electrolyte prepared in example 5.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the invention, all parts and percentages are weight units, and all equipment, raw materials and the like can be purchased from the market or are commonly used in the industry, if not specified.
Example 1
A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following specific steps:
(1) preparing a metal ion precursor solution of an oxide (garnet) ceramic fabric: adding 49 m mol of LiNO3，21 m molLa(NO3)3·6H2O，14 m mol ZrO(NO3)3·6H2O was dissolved in 40mL of absolute ethanol containing 5vol.% acetic acid, and 1.75 m mol Al (NO) was added3)3·9H2Taking O as an Al additive, and stirring for 24 hours at room temperature to form a uniform solution to obtain a precursor solution;
(2) preparation of oxide (garnet-type) ceramic fabrics: firstly, repeatedly washing and drying an undyed creped silk fabric by using deionized water and absolute ethyl alcohol to remove surface impurities; and (2) then, soaking the washed crepe silk fabric in the precursor solution in the step (1), stirring for 24 hours at 50 ℃, taking out, washing with absolute ethyl alcohol, and drying. And finally, placing the silk fabric soaked with the precursor solution in a tube furnace, calcining for 4 hours at 700 ℃ in the air, naturally cooling, taking out, and placing in a glove box filled with argon for later use to obtain Al-doped Li7La3Zr2O12(Al-LLZO) ceramic fabric. The X-ray electron diffraction (XRD) pattern of the Al-LLZO ceramic fabric is shown in figure 1.
(3) Preparing an organic polymer solid electrolyte solution: first, polyethylene oxide (PEO) was added to lithium perchlorate (LiClO) at 50 deg.C4) Vacuum drying at 100 deg.C for 24 hr; however, both are as EO: dissolving Li =10:1 in acetonitrile at a molar ratio, and finally stirring at room temperature for 48h to form a uniform mixed solution to obtain PEO-LiClO4A polymer solid electrolyte solution.
(4) Preparation of oxide (garnet type) ceramic fabric composite solid electrolyte: first, the PEO-LiClO of step (3) was drawn up with a syringe4The polymer solid electrolyte solution is poured into a polytetrafluoroethylene mold; then, the Al-LLZO ceramic fabric obtained in the step (2) is placed on a polytetrafluoroethylene mould which is fully paved with polymer solution, and a layer of PEO-LiClO is poured4Polymer solid electrolyte solution to form a sandwich structure; finally, wait for PEO-LiClO4And completely volatilizing acetonitrile in the polymer solid electrolyte solution, taking down the composite solid electrolyte membrane, and carrying out vacuum drying at 50 ℃ for 24h to obtain the final Al-LLZO ceramic fabric composite solid electrolyte membrane, wherein the total thickness of the obtained Al-LLZO ceramic fabric composite solid electrolyte membrane is controlled to be 100-120 mu m.
Example 2
A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following specific steps:
(1) preparing a metal ion precursor solution of an oxide (garnet) ceramic fabric: 45.5 m mol of LiNO3，21 m molLa(NO3)3·6H2O，10.5 m mol ZrO(NO3)3·6H2O was dissolved in stoichiometric ratio in 40mL of anhydrous ethanol containing 10 vol.% acetic acid, and 3.5 m mol of NbCl was added5As an Nb additive, stirring for 24 hours at room temperature to form a uniform solution;
(2) preparation of oxide (garnet-type) ceramic fabrics: firstly, repeatedly washing and drying a piece of undyed electric spinning silk fabric by using deionized water and absolute ethyl alcohol to remove surface impurities; and (2) soaking the cleaned electric spinning silk fabric in the precursor solution obtained in the step (1), stirring for 24 hours at 60 ℃, taking out, washing with absolute ethyl alcohol, and drying. And finally, placing the silk fabric soaked with the precursor solution in a tube furnace, calcining for 2.5 hours at 800 ℃ in the air, naturally cooling, taking out, and placing in a glove box filled with argon for later use to obtain Nb-doped Li7La3Zr2O12(Nb-LLZO) ceramic fabric. A Scanning Electron Microscope (SEM) photograph of the Nb-LLZO ceramic fabric is shown in FIG. 2.
(3) Preparing an organic polymer solid electrolyte solution: firstly, polyethylene oxide (PEO) is dried in vacuum at 50 ℃ and lithium chloride (LiCl) at 100 ℃ for 24 hours for standby; however, both are as EO: the molar ratio of Li =15:1 was dissolved in acetonitrile, and finally, the solution was stirred at room temperature for 48 hours to form a uniformly mixed solution, to obtain a PEO-LiCl polymer solid electrolyte solution.
(4) Preparation of oxide (garnet type) ceramic fabric composite solid electrolyte: firstly, sucking the PEO-LiCl polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the PEO-LiCl polymer solid electrolyte solution into a polytetrafluoroethylene mould; then, placing the Nb-LLZO ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mould fully paved with a polymer solution, and pouring a layer of PEO-LiCl polymer solid electrolyte solution to form a sandwich structure; and finally, after the acetonitrile in the PEO-LiCl polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain the final Nb-LLZO ceramic fabric composite solid electrolyte. The total thickness of the composite solid electrolyte membrane is controlled to be 100-120 mu m.
Example 3
A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following specific steps:
(1) preparing a metal ion precursor solution of an oxide (garnet) ceramic fabric: 45.5 m mol of LiNO3，21 m molLa(NO3)3·6H2O，10.5 m mol ZrO(NO3)3·6H2O was dissolved in stoichiometric ratio in 40mL of anhydrous ethanol containing 10 vol.% acetic acid, and 3.5 m mol of TaO (NO) was added3)3As Ta additive, and stirring for 24h at room temperature to form a uniform solution;
(2) preparation of oxide (garnet-type) ceramic fabrics: firstly, repeatedly washing and drying an undyed crepe satin plain silk fabric by using deionized water and absolute ethyl alcohol to remove surface impurities; and (2) soaking the cleaned crepe satin plain silk fabric in the precursor solution in the step (1), stirring for 24 hours at 60 ℃, taking out, washing with absolute ethyl alcohol, and drying. And finally, placing the silk fabric soaked with the precursor solution in a tube furnace, calcining for 2.5 hours at 800 ℃ in the air, naturally cooling, taking out, and placing in a glove box filled with argon for later use to obtain Ta doped with Li7La3Zr2O12(Ta-LLZO) ceramic fabric. An SEM photograph of the Ta-LLZO ceramic fabric is shown in FIG. 3.
(3) Preparing an organic polymer solid electrolyte solution: firstly, polyethylene oxide (PEO) is dried in vacuum for 24 hours at 50 ℃ and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) at 100 ℃ for standby; however, both are as EO: and (3) dissolving Li =8:1 in acetonitrile in a molar ratio, and finally stirring at room temperature for 48h to form a uniform mixed solution to obtain a PEO-LiTFSI polymer solid electrolyte solution.
(4) Preparation of oxide (garnet type) ceramic fabric composite solid electrolyte: firstly, sucking the PEO-LiTFSI polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the PEO-LiTFSI polymer solid electrolyte solution into a polytetrafluoroethylene mold; then, placing the Ta-LLZO ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mold fully paved with a polymer solution, and pouring a layer of PEO-LiTFSI polymer solid electrolyte solution to form a sandwich structure; and finally, after the acetonitrile in the PEO-LiTFSI polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and carrying out vacuum drying at 50 ℃ for 24 hours to obtain the final Ta-LLZO ceramic fabric composite solid electrolyte. The total thickness of the composite solid electrolyte membrane is controlled to be 120-140 μm. An SEM photograph of the Ta-LLZO ceramic fabric composite solid electrolyte is shown in FIG. 4.
As can be seen from FIGS. 2 and 3, the patterns of the resulting ceramic fabrics are different depending on the fabric texture of the silk fabric template.
Example 4
A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following specific steps:
(1) preparing a metal ion precursor solution of an oxide (garnet) ceramic fabric: 45.5 m mol of LiNO3，21 m molLa(NO3)3·6H2O，10.5 m mol ZrO(NO3)3·6H2O was dissolved in stoichiometric ratio in 40mL of anhydrous ethanol containing 10 vol.% acetic acid, and 3.5 m mol of TaO (NO) was added3)3As Ta additive, and stirring for 24h at room temperature to form a uniform solution;
(2) preparation of oxide (garnet-type) ceramic fabrics: firstly, repeatedly washing and drying a piece of undyed taffeta silk fabric by using deionized water and absolute ethyl alcohol to remove surface impurities; and (2) soaking the cleaned crepe satin plain silk fabric in the precursor solution in the step (1), stirring for 24 hours at 70 ℃, taking out, washing with absolute ethyl alcohol, and drying. Finally, placing the silk fabric soaked with the precursor solution in a tube furnace, calcining for 1.5h at 900 ℃ in the air, naturally cooling, taking out, and placing inFilling argon into the glove box for later use to obtain Ta doped Li7La3Zr2O12(Ta-LLZO) ceramic fabric.
(3) Preparing an organic polymer solid electrolyte solution: firstly, polyvinylidene fluoride (PVDF) is dried in vacuum for 24 hours at 80 ℃ and lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) at 100 ℃ for standby; however, both PVDF: and dissolving the LiTFSI =3:1 in acetonitrile, and finally stirring at room temperature for 48h to form a uniform mixed solution to obtain the PVDF-LiTFSI polymer solid electrolyte solution.
(4) Preparation of oxide (garnet type) ceramic fabric composite solid electrolyte: firstly, sucking the PVDF-LiTFSI polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the PVDF-LiTFSI polymer solid electrolyte solution into a polytetrafluoroethylene mold; then, placing the Ta-LLZO ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mold fully paved with a polymer solution, and then pouring a layer of PVDF-LiTFSI polymer solid electrolyte solution to form a sandwich structure; and finally, after the acetonitrile in the PVDF-LiTFSI polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and carrying out vacuum drying at 60 ℃ for 48 hours to obtain the final Ta-LLZO ceramic fabric composite solid electrolyte. The total thickness of the composite solid electrolyte membrane is controlled to be 130-
The Electrochemical Impedance Spectroscopy (EIS) of the stainless steel/solid electrolyte/stainless steel symmetrical battery of the Ta-LLZO ceramic fabric composite solid electrolyte prepared in the embodiment is shown in figure 5; the cycling performance of the Li/solid electrolyte/Li symmetric cell is shown in fig. 6.
Example 5
A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template comprises the following specific steps:
(1) preparing a metal ion precursor solution of an oxide (perovskite type) ceramic fabric: 23.1 m mol of LiNO3，38.9 La(NO3)3·6H2O，70 m mol Ti(OC4H9)4Dissolving the mixture in 40mL of absolute ethanol containing 15 vol.% of acetic acid according to the stoichiometric ratio, and stirring the mixture at room temperature for 24 hours to form a uniform solution;
(2) preparation of oxide (perovskite) ceramic fabrics: firstly, repeatedly washing and drying an undyed crepe satin plain silk fabric by using deionized water and absolute ethyl alcohol to remove surface impurities; and (2) soaking the cleaned crepe satin plain silk fabric in the precursor solution in the step (1), stirring for 24 hours at 70 ℃, taking out, washing with absolute ethyl alcohol, and drying. And finally, placing the silk fabric soaked with the precursor solution in a tube furnace, calcining for 2.5 hours at 800 ℃ in the air, naturally cooling, taking out, and placing in a glove box filled with argon for later use to obtain Li3xLa(2/3)-xTiO3(LLTO) ceramic fabrics.
(3) Preparing an organic polymer solid electrolyte solution: firstly, drying polyacrylonitrile in vacuum at 60 ℃ for 24 hours at 100 ℃ for later use, wherein the lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) is used as a precursor; however, both PAN: and dissolving the solid electrolyte solution of the PEO-LiTFSI polymer in acetonitrile at a ratio of LiTFSI =3:1, and finally stirring the solution at room temperature for 48 hours to form a uniform mixed solution.
(4) Preparation of oxide (garnet type) ceramic fabric composite solid electrolyte: firstly, sucking the PAN-LiTFSI polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the solution into a polytetrafluoroethylene mold; then, placing the LLTO ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mold fully paved with a polymer solution, and then pouring a layer of PAN-LiTFSI polymer solid electrolyte solution to form a sandwich structure; and finally, after the acetonitrile in the PAN-LiTFSI polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and carrying out vacuum drying at 60 ℃ for 48h to obtain the final LLTO ceramic fabric composite solid electrolyte.
The Electrochemical Impedance Spectrum (EIS) of the stainless steel/solid electrolyte/stainless steel symmetrical cell of the LLTO ceramic fabric composite solid electrolyte prepared in this example is shown in FIG. 7.
As can be seen from fig. 5 and 7, when the crystal types of the ceramic fabrics are different, the ionic conductivities of the composite solid electrolytes are also different.
XRD pattern of Al-LLZO ceramic fabric prepared in example 1The spectra are shown in FIG. 1, and all diffraction peaks are substantially in comparison with Li, as found by a standard garnet crystal form card5La3Nb2O12Standard peak matching with a small number of hetero-peaks corresponding to La2Zr2O7This is probably due to Li volatilization at high temperature.
SEM photographs of the oxide garnet-type ceramic fabrics prepared in examples 2 and 3 are shown in fig. 2 and 3, respectively. The ceramic fabric well keeps the appearance of an original silk fabric template, has a unique weaving structure of a textile and keeps fibers intact. In addition, the ceramic fibers are loose and porous, which is extremely advantageous for the subsequent casting and infiltration of the organic polymer solid electrolyte solution into the ceramic fabric network. Meanwhile, the shapes of the ceramic fabrics derived from the silk fabric template fabrics are different due to different types of the silk fabric.
SEM photograph of Ta-LLZO ceramic fabric composite solid electrolyte prepared in example 3 As shown in FIG. 4, the surface of the ceramic fabric composite solid electrolyte was smooth and had many pores due to acetonitrile volatilization during casting of PEO-LiTFSI polymer solid electrolyte solution.
EIS of stainless steel/solid electrolyte/stainless steel symmetrical cells of garnet-type and perovskite-type ceramic fabric composite solid electrolyte prepared in examples 4 and 5 are shown in FIGS. 5 and 7, respectively, from which it can be seen that the ionic conductivity of the composite solid electrolyte is improved as the test temperature is increased, wherein the ionic conductivity of Ta-LLZO ceramic fabric composite solid electrolyte at 30 ℃ is 8.89 × 10-5S cm-1The high ionic conductivity is attributed to the fact that the 3D ceramic fabric network can provide a long continuous ion-guiding path. In addition, the ionic conductivity of the garnet-type ceramic fabric composite solid electrolyte is higher than that of the perovskite-type electrolyte, which is due to the fact that the electrochemical performance can be optimized due to the doping of hetero atoms in the garnet-type ceramic fabric.
The cycling performance of the Li/solid electrolyte/Li symmetric battery of Ta-LLZO ceramic fabric composite solid electrolyte prepared in example 4 is shown in FIG. 6. As can be seen, the symmetric cell is 300 μ A cm-2Can stably circulate for 180h without current densityShort circuit, the voltage plateau of which is also only 0.12V, indicates excellent interfacial stability between the Ta-LLZO ceramic fabric composite solid electrolyte and lithium metal.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A method for preparing an oxide type ceramic fabric composite solid electrolyte by taking silk fabric as a sacrificial template is characterized by comprising the following steps:
(1) preparing an oxide type ceramic solid electrolyte metal ion precursor solution: dissolving metal ion precursor salt containing oxide type ceramic solid electrolyte into a proper amount of acetic acid-absolute ethyl alcohol solution, adding a proper amount of hetero-atom precursor salt as a doping agent, and stirring at room temperature to form a uniform solution;
(2) preparation of oxide type ceramic fabric:
washing undyed silk fabric with deionized water and absolute ethyl alcohol, drying, and removing surface impurities;
soaking the cleaned silk fabric in the precursor solution obtained in the step (1), fully stirring, washing with absolute ethyl alcohol, and drying;
placing the silk fabric soaked with the precursor solution in a tubular furnace, calcining at 600-1000 ℃ for 2-6h in air, naturally cooling, taking out the oxide type ceramic fabric, and placing the oxide type ceramic fabric in a glove box filled with argon for later use;
(3) preparing an organic polymer solid electrolyte solution:
selecting a polymer capable of being used as a solid electrolyte and a conductive lithium salt, and respectively drying the polymer and the conductive lithium salt in vacuum within the temperature range below the respective melting points for later use;
dissolving a polymer and a conductive lithium salt in acetonitrile, and fully stirring at room temperature to form a uniformly mixed organic polymer solid electrolyte solution;
(4) preparing an oxide type ceramic fabric composite solid electrolyte:
sucking the organic polymer solid electrolyte solution in the step (3) by using a syringe, and pouring the solution into a mould;
placing the oxide type ceramic fabric obtained in the step (2) on a polytetrafluoroethylene mould fully paved with a polymer solution, and pouring a layer of organic polymer solid electrolyte solution to form a sandwich structure;
and when the acetonitrile in the organic polymer solid electrolyte solution is completely volatilized, taking down the composite solid electrolyte membrane, and drying at the temperature of 40-70 ℃ for 12-48h to obtain the oxide type ceramic fabric composite solid electrolyte.
2. The method of claim 1, wherein: the metal ion precursor salt in the step (1) is selected from precursor salts required by garnet type, NASICON type, perovskite type or anti-perovskite type ceramics, and the heterogeneous atom precursor salt is selected from Al salt, Nb salt or Ta salt.
3. The method of claim 1, wherein: the calcination temperature of the silk fabric soaked with the precursor liquid in the step (2) is 700-900 ℃, and the calcination time is 2-4 h.
4. The method of claim 1, wherein: the polymer in the step (3) is selected from one or a mixture of more polymers of polyethylene oxide (PEO), Polyacrylonitrile (PAN) polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF) and polyvinyl chloride (PVC),
the conductive lithium salt is selected from lithium halide (LiX, X = F, Cl, Br, I), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Or lithium tetrafluoroborate (LiBF)4) One or more of them.
5. The method of claim 1, wherein: the content of acetic acid in the acetic acid-absolute ethyl alcohol solution in the step (1) is 5-25 vol.%.
6. The method of claim 1, wherein: the tissue structure of the silk fabric in the step (2) is double-crepe, crepe satin, electric power spinning, doupion silk, taffeta silk, twill silk, georgette or Dongfeng yarn.
7. The method of claim 1, wherein: and (3) after the silk fabric is soaked in the precursor solution in the step (2), stirring at the temperature of 50-70 ℃ for 2-6 h.
8. The method of claim 1, wherein: and (3) stirring the polymer and the conductive lithium salt in the acetonitrile for 24-48 h.
9. The method of claim 1, wherein: and (4) drying the composite solid electrolyte membrane in the step (4) at the temperature of 50-60 ℃ for 24-48 h.
10. An oxide type ceramic fabric composite solid electrolyte for a flexible solid lithium battery, which is prepared by the preparation method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2462643A1 (en) * | 2009-08-07 | 2012-06-13 | Powergenix Systems, Inc. | Carbon fiber zinc negative electrode |
| CN106457214A (en) * | 2014-06-11 | 2017-02-22 | 贺利氏德国有限及两合公司 | Supported catalyst and method for producing a porous graphitized carbon material covered with metal nanoparticles |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN110088969A (en) * | 2016-11-08 | 2019-08-02 | 菲斯科公司 | All solid state Li ion battery and its manufacturing method comprising mechanical flexibility ceramic electrolyte |
| US10454118B2 (en) * | 2008-12-08 | 2019-10-22 | Nexceris Innovation Holdings, Llc | Current collectors for solid oxide fuel cell stacks |
| CN110492170A (en) * | 2019-08-30 | 2019-11-22 | 电子科技大学 | A kind of high ionic conductivity composite solid electrolyte and preparation method thereof |
| US20200112050A1 (en) * | 2017-03-29 | 2020-04-09 | University Of Maryland, College Park | Solid-state hybrid electrolytes, methods of making same, and uses thereof |
-
2020
- 2020-06-23 CN CN202010585373.5A patent/CN111725562B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10454118B2 (en) * | 2008-12-08 | 2019-10-22 | Nexceris Innovation Holdings, Llc | Current collectors for solid oxide fuel cell stacks |
| EP2462643A1 (en) * | 2009-08-07 | 2012-06-13 | Powergenix Systems, Inc. | Carbon fiber zinc negative electrode |
| CN106457214A (en) * | 2014-06-11 | 2017-02-22 | 贺利氏德国有限及两合公司 | Supported catalyst and method for producing a porous graphitized carbon material covered with metal nanoparticles |
| CN110088969A (en) * | 2016-11-08 | 2019-08-02 | 菲斯科公司 | All solid state Li ion battery and its manufacturing method comprising mechanical flexibility ceramic electrolyte |
| US20200112050A1 (en) * | 2017-03-29 | 2020-04-09 | University Of Maryland, College Park | Solid-state hybrid electrolytes, methods of making same, and uses thereof |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
| CN110492170A (en) * | 2019-08-30 | 2019-11-22 | 电子科技大学 | A kind of high ionic conductivity composite solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 彭程等: "燃烧法制备中温SOFC电解质及其电极材料", 《稀有金属材料与工程》 * |
| 程晓琪 等: "蚕丝/聚氧化乙烯复合固态聚合物电解质", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078351A (en) * | 2021-03-29 | 2021-07-06 | 珠海冠宇电池股份有限公司 | Solid electrolyte, preparation method thereof and solid battery |
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