CN114243097A - NASICON type sodium ion ceramic electrolyte and preparation method thereof - Google Patents

NASICON type sodium ion ceramic electrolyte and preparation method thereof Download PDF

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CN114243097A
CN114243097A CN202111556399.8A CN202111556399A CN114243097A CN 114243097 A CN114243097 A CN 114243097A CN 202111556399 A CN202111556399 A CN 202111556399A CN 114243097 A CN114243097 A CN 114243097A
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copper
ceramic electrolyte
nasicon
sodium ion
sodium
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赵永杰
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Beijing Institute of Technology BIT
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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
    • H01M10/054—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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses an NASICON type sodium ion ceramic electrolyte and a preparation method thereof, wherein the NASICON type sodium ion ceramic electrolyte provided by the invention comprises the specific component of Na1+xZr2SixP3‑ xO12‑y Cu2+The compound, wherein x is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%. Cu2+Partial substitution of Zr in three-dimensional NASICON matrix structure4+The position of (2) can optimize a sodium ion transmission channel in the matrix framework structure, reduce the binding force and activation energy of sodium ion migration, and obviously improve the ionic conductivity of the ceramic electrolyte. In addition to this, Cu in the NASICON matrix lattice and at grain boundaries due to doping substitution2+The self-reduction stabilization mechanism can effectively improve the interface stability of the NASICON type ceramic electrolyte and the sodium metal electrode and obviously reduce the interface resistance. The all-solid-state sodium metal battery assembled by the ceramic electrolyte prepared by the method is further improvedThe electrochemical performance of the all-solid-state sodium metal battery is improved, and the NASICON type sodium ion ceramic electrolyte has excellent application prospect in the all-solid-state sodium metal battery.

Description

NASICON type sodium ion ceramic electrolyte and preparation method thereof
Technical Field
The invention relates to the field of functional conductive ceramics and the field of all-solid-state metal batteries, and mainly relates to an NASICON type sodium ion ceramic electrolyte and a preparation method thereof.
Background
Sodium ion batteries are receiving much attention from the green energy field due to their excellent safety characteristics, abundant sodium resource reserves and relatively high energy density, compared to lithium ion batteries that have been successfully commercialized. In solid state metal batteries, solid state electrolytes are used to replace conventional organic materials that are flammableThe liquid electrolyte can greatly improve the safety of the battery. In addition, the solid electrolyte, especially the oxide-based ceramic electrolyte, has higher elastic modulus, and can obstruct the extension of metal dendrite to a certain extent and avoid the short circuit of the solid battery. High energy density sodium metal (1166mAh g) may be employed in all solid state batteries-1) As a negative electrode, the energy density of the battery is further improved, and the battery has important potential application in the fields of distributed energy storage systems, household energy storage devices, low-speed electric vehicles, smart grid energy storage systems and the like.
At present, the solution for the large contact resistance of the interface between the solid electrolyte and the metal electrode in the all-solid-state metal battery is mainly solved to different degrees by adding liquid electrolyte or ionic liquid at the interface, introducing a beneficial interface layer, applying external pressure and the like. Although such methods have some effects on reducing the interface resistance and improving the interface compatibility, the stable cycle of the all-solid-state battery with safety, long-term and high efficiency cannot be realized. In addition, the consistency and repeatability of the processes are not high, and some technologies have relatively high requirements on experimental equipment and operating environments, so that the processes cannot be scaled. Sodium super ion conductors (NASICON) Na proposed by researchers1+xZr2SixP3-xO12(x is more than or equal to 0 and less than or equal to 2) as a solid electrolyte. It is receiving wide attention from researchers of materials due to its relatively excellent ion conducting characteristics, stable chemical properties, and wide electrochemical window. When x is 2, (i.e. Na)3Zr2Si2PO12) Has high ionic conductivity up to 10 at room temperature-4S cm-1But still has significantly lower ionic conductivity than conventional liquid electrolytes (10)-2S cm-1) And the preparation temperature range is severer.
Therefore, the following defects are mainly found in the current solid electrolyte and preparation for all-solid-state metal batteries: (1) the prepared solid electrolyte has low ionic conductivity, large interface contact resistance and poor interface compatibility with a solid electrode (a high-energy-density metal cathode and a high-working-voltage anode material); (2) the sintering temperature is too high, the preparation cost is too high, and the preparation method is difficult to scale in the preparation process.
Considering that the solid electrolyte in the prior art cannot meet our needs, the technical problems that need to be urgently solved by those skilled in the art are: there is a need to prepare a ceramic electrolyte material with high sodium ion conductivity at a relatively low sintering temperature, and at the same time, the ceramic electrolyte material shows lower interfacial resistance and better interfacial compatibility relative to a sodium metal negative electrode, so that an all-solid-state sodium metal battery assembled on the basis of the ceramic electrolyte shows excellent electrochemical performance.
Disclosure of Invention
In order to solve the problems, the invention provides an NASICON type sodium ion ceramic electrolyte and a preparation method thereof. The specific contents are as follows:
in a first aspect, the invention provides a sodium ion ceramic electrolyte of NASICON type, the matrix structure of which is doped with copper ions, and the copper ions partially replace Zr in the NASICON structure4+The position of (a).
Preferably, the matrix is Na1+xZr2SixP3-xO12(ii) a The chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+A compound; wherein x is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
Preferably, the copper ions are derived from one or more of the following copper-containing compounds: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
Preferably, the mass ratio of the matrix of the NASICON type sodium ion ceramic electrolyte to the copper ions is 100: 0-1.
In a second aspect, the present invention provides a method for preparing the NASICON type sodium ion ceramic electrolyte of the first aspect, wherein the substrate Na is1+xZr2SixP3-xO12Adding inThe copper-based sintering aid is obtained by the following specific method:
step 1, obtaining a raw material used as the substrate, wherein the raw material comprises a plurality of compounds and copper-containing compounds;
weighing the various compounds and the copper-containing compound according to the mass ratio of 100: 0-1, and carrying out ball milling and mixing; the various compounds are according to the formula Na1+xZr2SixP3-xO12Weighing, wherein x is more than or equal to 1.8 and less than or equal to 2.2;
wherein the plurality of compounds comprise a sodium source compound, a zirconium source compound, a silicon source compound, a phosphorus source compound;
step 2, drying the raw material mixed with the copper-containing compound obtained in the step 1, preserving heat at 800-1000 ℃, and presintering;
step 3, preparing the pre-sintered raw material obtained in the step 2 into a green sheet;
step 4, sintering the green sheet at high temperature to obtain copper ion doped NASICON type sodium ion ceramic electrolyte; wherein the matrix structure is doped with copper ions, and the copper ions partially replace Zr in the NASICON structure4+The position of (a);
wherein the chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+X is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
Preferably, the sodium source compound is one or more of sodium acetate, sodium oxalate, sodium carbonate, sodium nitrate, sodium isopropoxide, sodium oxide and sodium hydroxide; the zirconium source compound is one or more of zirconium oxide, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium acetate and zirconium hydroxide.
Preferably, the silicon source compound comprises one or more of silicon dioxide, orthosilicate ester, tetraethoxysilane, propyl orthosilicate, silicic acid, silicone oil and tetramethyl orthosilicate; the phosphorus source compound comprises one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide and phosphoric acid.
Preferably, the copper-containing compound comprises one or more of: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
Preferably, in the step 4, the green sheet is sintered at high temperature to obtain a copper ion doped NASICON type sodium ion ceramic electrolyte, which includes: and (3) insulating the green sheet at 1000-1200 ℃ for 5-24 h, and sintering at high temperature to obtain the copper ion doped NASICON type sodium ion ceramic electrolyte.
In a third aspect, the present invention provides an all-solid-state sodium metal battery comprising a NASICON-type sodium ion ceramic electrolyte according to any one of the above first aspects.
Compared with the prior art, the embodiment of the invention has the following advantages:
the embodiment of the application provides an NASICON type sodium ion ceramic electrolyte and a preparation method thereof. The NASICON type sodium ion ceramic electrolyte is prepared by Zr in a three-dimensional NASICON structure4+Partially replace Cu at the position of (2)2+. On one hand, during sintering, point defects caused by copper ion doping substitution help to promote mass transfer; meanwhile, due to the liquid phase sintering effect of the copper ion compound, the densification of the ceramic matrix can be realized at a relatively low sintering temperature, and further the binding force and activation energy of sodium ion migration can be reduced. Thereby significantly improving the ionic conductivity of the ceramic electrolyte compared with the ceramic electrolyte before doping. On the other hand, Cu at grain boundaries is neutralized by the NASICON matrix lattice2+The self-reduction stabilization mechanism can effectively improve the interface stability of the NASICON type ceramic electrolyte to the sodium metal electrode and obviously reduce the contact resistance between the interfaces. The all-solid-state sodium metal battery assembled on the basis of the ceramic electrolyte provided by the embodiment of the application has excellent electrochemical performance.
Drawings
FIG. 1 is a flow chart of a method of preparing a NASICON type sodium ion ceramic electrolyte and a method of preparing the same according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of a NASICON type sodium ion solid state ceramic electrolyte prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a cross section of a NASICON type sodium ion ceramic electrolyte prepared in example 1 of the present invention;
FIG. 4 is an EIS spectrum of a NASICON type sodium ion solid state ceramic electrolyte prepared in example 1 of the present invention;
FIG. 5 is a graph showing the change in the impedance spectrum of a NASICON type sodium ion ceramic electrolyte prepared in example 1 of the present invention for sodium metal;
FIG. 6 is an XRD pattern of a copper ion doped NASICON type sodium ion solid state ceramic electrolyte prepared in example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of a cross section of a copper ion-doped NASICON type sodium ion ceramic electrolyte prepared in example 2 of the present invention;
FIG. 8 is an EIS spectrum of a copper ion doped NASICON type sodium ion ceramic electrolyte prepared in example 2 of the present invention;
FIG. 9 is a graph showing the change in the impedance spectrum of a copper ion-doped NASICON type sodium ion ceramic electrolyte for sodium metal prepared in example 2 of the present invention;
FIG. 10 is a scanning electron micrograph of a cross section of a copper ion-doped NASICON type sodium ion ceramic electrolyte prepared in example 3 of the present invention;
FIG. 11 is an XRD pattern of a copper ion doped NASICON type sodium ion solid state ceramic electrolyte prepared in example 3 of the present invention;
FIG. 12 is a scanning electron micrograph of a cross section of a copper ion-doped NASICON type sodium ion ceramic electrolyte prepared in example 4 of the present invention;
fig. 13 is an XRD pattern of copper ion-doped NASICON-type sodium ion solid-state ceramic electrolyte prepared in example 4 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but the present invention should not be construed as being limited thereto. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The present invention employs, unless otherwise indicated, examples of reagents, methods and apparatus conventional in the art.
In a first aspect, embodiments of the present invention provide a sodium ion ceramic electrolyte of NASICON type, in which a matrix structure of the sodium ion ceramic electrolyte of NASICON type is doped with copper ions, and the copper ions partially replace Zr in the NASICON structure4+The position of (a).
Copper ions are doped into the NASICON type sodium ion ceramic electrolyte matrix and partially replace Zr in the NASICON lattice structure4+The position of (a).
Preferably, the matrix is Na1+xZr2SixP3-xO12(ii) a The chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+A compound; wherein x is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
Preferably, the copper ions are derived from one or more of the following copper-containing compounds: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
In practice, copper oxide, copper fluoride and copper nitrate may be selected as the source of copper ions.
Preferably, the mass ratio of the matrix to the copper ions is 100: 0-1.
In the NASICON type sodium ion ceramic electrolyte matrix structure provided by the invention, copper ions partially replace Zr in the NASICON structure4+The point defects caused by copper ion doping substitution during sintering help to promote mass transfer; meanwhile, the densification of the ceramic matrix can be realized at a relatively low sintering temperature due to the liquid phase sintering effect of the copper ion compound, and the copper ion is doped to replace Zr4+Can optimize the sodium ion transmission channel in the matrix frame and reduce the binding force and activation energy of sodium ion migration. Thus, the ion conductivity of the ceramic electrolyte is significantly improved compared to the ceramic electrolyte before doping.
In addition, Cu at grain boundaries is neutralized by the NASICON matrix lattice2+The self-reduction stabilization mechanism effectively improves the interface compatibility of the NASICON type ceramic electrolyte to the sodium metal electrode and obviously reduces the contact resistance between the interfaces. The all-solid-state sodium metal battery assembled on the basis of the ceramic electrolyte provided by the embodiment of the application has excellent electrochemical performance.
In a second aspect, the present invention provides a method for preparing the NASICON type sodium ion ceramic electrolyte of the first aspect, wherein the substrate Na is1+xZr2SixP3-xO12The copper-based sintering aid is added to obtain the copper-based sintering aid through solid-phase reaction, and the method specifically comprises the following steps:
a step S1 of obtaining a raw material used as the base, the raw material including a plurality of compounds and a copper-containing compound;
weighing the various compounds and the copper-containing compound according to the mass ratio of 100: 0-1, and carrying out ball milling and mixing; the various compounds are according to the formula Na1+xZr2SixP3-xO12Weighing, wherein x is more than or equal to 1.8 and less than or equal to 2.2;
wherein the plurality of compounds comprise a sodium source compound, a zirconium source compound, a silicon source compound, a phosphorus source compound;
preferably, the sodium source compound is one or more of sodium acetate, sodium oxalate, sodium carbonate, sodium nitrate, sodium isopropoxide, sodium oxide and sodium hydroxide; the zirconium source compound is one or more of zirconium oxide, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium acetate and zirconium hydroxide.
Preferably, the silicon source compound comprises one or more of silicon dioxide, orthosilicate ester, tetraethoxysilane, propyl orthosilicate, silicic acid, silicone oil and tetramethyl orthosilicate; the phosphorus source compound comprises one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide and phosphoric acid.
Preferably, the copper-containing compound comprises one or more of: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
In specific implementation, the sodium source compound, the zirconium source compound, the silicon source compound, the phosphorus source compound and the copper source compound are mixed according to a chemical formula Na1+xZr2SixP3-xO12-y Cu2+Weighing raw materials of a copper-based compound (x is more than or equal to 1.8 and less than or equal to 2.2, y is more than 0 and less than 1 wt%), and performing ball milling and mixing uniformly by taking ethanol as a grinding medium, wherein the ball milling time is 6-24 hours.
And step S2, drying the raw material mixed with the copper-containing compound obtained in the step 1, preserving heat at 800-1000 ℃, and pre-sintering.
Specifically, the raw materials after ball milling discharging are placed in an oven at 80 ℃ for drying, the powder obtained after drying is placed in an alumina crucible, heat preservation is carried out for 5-10 hours at 800-1000 ℃, and presintering is carried out, wherein the temperature rise rate of the presintering is 1-10 ℃ min-1。
Step S3, preparing the pre-sintered raw material obtained in step 2 into a green sheet.
In the specific implementation, the pre-sintered powder is subjected to secondary ball milling, the ball milling discharging is performed, then the drying is performed, the powder is subjected to tabletting and forming after granulation, and the green blank sheet is obtained, wherein the ball milling time is 6-24 hours, and the pressure for tabletting and forming is 5-20 MPa.
Step S4, sintering the green sheet at high temperature to obtain NASICON type sodium ion ceramic electrolyte doped with copper ions; wherein the structure of the matrix is doped with copper ions, and the copper ions partially replace Zr in a NASICON structure4+The position of (a);
wherein the chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+X is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
Preferably, in the step 4, the green sheet is sintered at high temperature to obtain a copper ion doped NASICON type sodium ion ceramic electrolyte, which includes: and (3) insulating the green sheet at 1000-1200 ℃ for 5-24 h, and sintering at high temperature to obtain the copper ion doped NASICON type sodium ion ceramic electrolyte.
In specific implementation, the heating rate of the high-temperature sintering is 1-10 ℃ min-1. When the green sheet is in a high-temperature sintering process, the point defects caused by doping substitution help to promote mass transfer, and simultaneously, the densification of the ceramic matrix can be realized at a relatively low sintering temperature due to the liquid-phase sintering effect of the copper ion compound.
In a third aspect, the present invention provides an all-solid-state sodium metal battery comprising a NASICON-type sodium ion ceramic electrolyte according to any one of the above first aspects.
In order that those skilled in the art may better understand the present invention, the following description will illustrate the preparation method provided by the present invention by means of a number of specific examples.
The effects of the present application will be fully described first in terms of a control group (example 1) and an experimental group (example 2).
Example 1
The control group is NASICON type sodium ion ceramic electrolyte in the related art, and the preparation process of the control group is as follows:
mixing sodium acetate, zirconium acetate, silicon dioxide, ammonium dihydrogen phosphate, and Na3Zr2Si2PO12The raw materials are weighed according to the stoichiometric ratio, and are put into absolute ethyl alcohol for ball milling and mixing, wherein the rotating speed of the ball mill is 300r min-1The ball milling time is 12 h;
after ball milling and discharging, placing the material in an oven at 80 ℃ for drying, and then preserving heat for 10 hours at 1000 ℃ for presintering;
carrying out secondary ball milling on the pre-sintered powder for 12h, drying the powder in an oven, and pressing the powder into green sheets with the diameter of 10mm and the thickness of 1mm by using the pressure of 10 MPa;
the green sheet is sintered by keeping the temperature at 1250 ℃ for 10h, and the heating rate is 200 ℃ for h-1Obtaining NASICON type Na3Zr2Si2PO12A ceramic electrolyte.
FIG. 1 is a SEM photograph showing the cross-section of the ceramic electrolyte sheet obtained in this example, wherein the distribution of the grain size in the microstructure is relatively broadThe presence of pores was clearly observed. As shown in FIG. 2, which is an XRD pattern of the ceramic electrolyte sheet obtained in this example, the ceramic sample obtained was a monoclinic phase, and ZrO which was a hetero-phase was clearly observed2The associated diffraction peaks.
And (3) polishing two surfaces of the obtained ceramic electrolyte sheet by using a series of sand papers with different meshes until the mirror surface is smooth, spraying gold on the two surfaces, measuring the ionic conductivity by using an alternating current impedance method, wherein the frequency test interval is 1M-0.1 Hz. As shown in FIG. 3, the room temperature ionic conductivity of the pure NASICON type ceramic electrolyte was 8.4X 10-4S cm-1。
To evaluate the interfacial compatibility of the ceramic electrolyte with the sodium metal electrode, a button-2032 sodium-sodium symmetric cell was assembled with a ceramic wafer as the electrolyte, and the sodium metal electrode had an area of about 0.3cm2. The interface stability of the ceramic electrolyte and the sodium metal electrode was studied using an electrochemical workstation.
As shown in fig. 4, the electrolyte-sodium metal interface resistance increased significantly over time, indicating very poor interface stability between the two.
Example 2
Experimental group the NASICON type sodium ion ceramic electrolytes of the present application were prepared as follows:
mixing sodium acetate, zirconium acetate, silicon dioxide, ammonium dihydrogen phosphate, copper oxide, and Na3Zr2Si2PO12The raw materials are weighed according to the stoichiometric ratio of-0.75 wt% of CuO, and are put into absolute ethyl alcohol for ball milling and mixing, and the rotating speed of a ball mill is 300rmin-1The ball milling time is 12 h;
after ball milling and discharging, placing the material in an oven at 80 ℃ for drying, and then preserving heat for 10 hours at 1000 ℃ for presintering;
carrying out secondary ball milling on the pre-sintered powder for 12h, drying the powder in an oven, and pressing the powder into green sheets with the diameter of 10mm and the thickness of 1mm by using the pressure of 10 MPa;
the green blank sheet is sintered by keeping the temperature at 1150 ℃ for 10h and the heating rate is 200 ℃ for h-1To obtain Cu2+Doped NASICON-type sodium ion ceramic electrolytes.
To ceramic electrolyteThe slice section is subjected to electron microscope scanning analysis, and the result is shown in figure 5, and the density of the matrix can be remarkably improved due to the transition liquid phase sintering effect of CuO; FIG. 6 shows Cu obtained in example 22+XRD pattern of doped NASICON type sodium ion ceramic electrolyte, the resulting electrolyte is still monoclinic and contains a small amount of hetero-phase ZrO2。
And (3) polishing two surfaces of the obtained ceramic electrolyte sheet by using a series of sand papers with different meshes until the mirror surface is smooth, spraying gold on the two surfaces, measuring the ionic conductivity by using an alternating current impedance method, wherein the frequency test interval is 1M-0.1 Hz. As shown in FIG. 7, Cu2+The doped NASICON-type ceramic electrolyte has a room temperature ionic conductivity of 1.74X 10-3S cm-1。
To evaluate the interfacial compatibility of the ceramic electrolyte with the sodium metal electrode, a button-2032 sodium-sodium symmetric cell was assembled with a ceramic wafer as the electrolyte, and the sodium metal electrode had an area of about 0.3cm2. The interface stability of the ceramic electrolyte and the sodium metal electrode was studied using an electrochemical workstation.
As shown in fig. 8, the overall resistance change of the symmetric cell was insignificant over a long period of rest time.
This example illustrates that in Na, compared to the control group1+xZr2SixP3-xO12The addition of the copper-based sintering aid in the matrix enables the electrolyte-sodium metal to have excellent interface compatibility, which is precisely due to the fact that Cu is in lattice and grain boundary of NASICON matrix2+The self-reduction stabilization mechanism effectively improves the interface stability of the NASICON type ceramic electrolyte to the sodium metal electrode and obviously reduces the contact resistance between the interfaces.
Meanwhile, NASICON type sodium ion ceramic electrolyte is prepared by Zr in three-dimensional NASICON structure4+Partially replace Cu at the position of (2)2+During sintering, point defects caused by copper ion doping substitution help to promote mass transfer; meanwhile, due to the liquid phase sintering effect of the copper ion compound, the densification of the ceramic matrix can be realized at a relatively low sintering temperature, so that the binding force and the activation energy of the sodium ion migration can be reduced. Thus, the ionic conductivity of the ceramic electrolyte is made comparable to dopingThe front ceramic electrolyte is remarkably improved.
Example 3
This example provides a process for the preparation of NASICON-type sodium ion ceramic electrolytes from copper fluoride as the source of copper ions:
sodium carbonate, zirconium acetate, silicon dioxide, ammonium dihydrogen phosphate and copper fluoride are mixed according to Na3Zr2Si2PO12Weighing the raw materials according to the stoichiometric ratio of-0.5 wt% of copper fluoride, and putting the raw materials into absolute ethyl alcohol for ball milling and mixing, wherein the rotating speed of a ball mill is 300r min-1The ball milling time is 12 h;
after ball milling and discharging, placing the material in an oven at 80 ℃ for drying, and then preserving heat for 10 hours at 1000 ℃ for presintering;
performing secondary ball milling on the obtained pre-sintered block, drying and pressing the powder into a wafer with the diameter of 10mm and the thickness of 1 mm;
the molding sheet is sintered at 1050-1200 ℃ for 10h, and the heating rate is 200 ℃ for h-1To obtain Cu2+Doped Na3Zr2Si2PO12Sodium ion ceramic electrolytes.
The cross section of the ceramic electrolyte sheet was analyzed by scanning electron microscopy, and the results are shown in FIG. 10. Under the effect of copper fluoride, compared with fig. 3, the compactness of the ceramic matrix is obviously improved, and the grain size distribution is more uniform.
FIG. 11 shows Cu obtained in example 32+XRD pattern of doped NASICON type sodium ion ceramic electrolyte, the resulting electrolyte still being in monoclinic phase and containing a small amount of hetero-phase ZrO2。
Example 4
This example provides a process for the preparation of NASICON-type sodium ion ceramic electrolytes from copper nitrate as the source of copper ions:
sodium carbonate, zirconyl nitrate, silicon dioxide, ammonium dihydrogen phosphate and cupric nitrate are mixed according to Na3Zr2Si2PO12-0.5 wt% copper nitrate, by weight, in a stoichiometric ratio, and ball-milling and mixing the mixture in absolute ethanol at a ball mill rotation speed of 300rmin-1Ball milling time of 12h；
After ball milling and discharging, placing the material in an oven at 80 ℃ for drying, and then preserving heat for 10 hours at 1000 ℃ for presintering;
performing secondary ball milling on the obtained pre-sintered block, drying and pressing the powder into a wafer with the diameter of 10mm and the thickness of 1 mm;
the molding sheet is sintered at 1050-1200 ℃ for 10h, and the heating rate is 200 ℃ for h-1To obtain Cu2+Doped Na3Zr2Si2PO12Sodium ion ceramic electrolytes.
The cross section of the ceramic electrolyte sheet was analyzed by scanning electron microscopy, and the results are shown in FIG. 12. Under the effect of copper fluoride, compared with fig. 3, the compactness of the ceramic matrix is obviously improved, and the grain size distribution is more uniform.
FIG. 13 shows Cu obtained in example 32+XRD pattern of doped NASICON type sodium ion ceramic electrolyte, the resulting electrolyte still being in monoclinic phase and containing a small amount of hetero-phase ZrO2。
For simplicity of explanation, the method embodiments are described as a series of acts or combinations, but those skilled in the art will appreciate that the present invention is not limited by the order of acts, as some steps may occur in other orders or concurrently in accordance with the invention. Further, those skilled in the art will appreciate that the embodiments described in the specification are preferred embodiments and that the acts and elements referred to are not necessarily required to practice the invention.
The NASICON type sodium ion ceramic electrolyte and the preparation method thereof provided by the invention are described in detail above, and the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (10)

1. The NASICON type sodium ion ceramic electrolyte is characterized in that a matrix structure of the NASICON type sodium ion ceramic electrolyte is doped with copper ions, and the copper ions partially replace Zr in the NASICON structure4+The position of (a).
2. The NASICON-type sodium ion ceramic electrolyte of claim 1, wherein the matrix is Na1+ xZr2SixP3-xO12(ii) a The chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+A compound;
wherein x is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
3. The NASICON-type sodium ion ceramic electrolyte of claim 1, wherein the copper ions are derived from one or more of the following copper-containing compounds: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
4. The NASICON-type sodium ion ceramic electrolyte according to claim 1, wherein the mass ratio of the matrix to the copper ions is 100: 0-1.
5. A method of preparing the NASICON type sodium ion ceramic electrolyte according to any of the above claims 1-4, characterized in that in the matrix Na1+xZr2SixP3-xO12The copper-based sintering aid is added, and the specific method comprises the following steps:
step 1, obtaining a raw material used as the substrate, wherein the raw material comprises a plurality of compounds and copper-containing compounds;
weighing the various compounds and the copper-containing compound according to the mass ratio of 100: 0-1, and carrying out ball milling and mixing; the various compounds are according to the formula Na1+xZr2SixP3-xO12Weighing, wherein x is more than or equal to 1.8 and less than or equal to 2.2;
wherein the plurality of compounds comprise a sodium source compound, a zirconium source compound, a silicon source compound, a phosphorus source compound;
step 2, drying the raw material mixed with the copper-containing compound obtained in the step 1, preserving heat at 800-1000 ℃, and presintering;
step 3, preparing the pre-sintered raw material obtained in the step 2 into a green sheet;
step 4, sintering the green sheet at high temperature to obtain copper ion doped NASICON type sodium ion ceramic electrolyte; wherein the matrix structure is doped with copper ions, and the copper ions partially replace Zr in the NASICON structure4+The position of (a);
wherein the chemical general formula of the NASICON type sodium ion ceramic electrolyte is Na1+xZr2SixP3-xO12-y Cu2+X is more than or equal to 1.8 and less than or equal to 2.2, and y is more than 0 and less than 1 wt%.
6. The preparation method according to claim 5, wherein the sodium source compound is one or more of sodium acetate, sodium oxalate, sodium carbonate, sodium nitrate, sodium isopropoxide, sodium oxide and sodium hydroxide; the zirconium source compound is one or more of zirconium oxide, zirconyl nitrate, zirconium oxychloride, zirconium acetylacetonate, zirconium acetate and zirconium hydroxide.
7. The preparation method according to claim 5, wherein the silicon source compound comprises one or more of silicon dioxide, orthosilicate ester, tetraethoxysilane, propyl orthosilicate, silicic acid, silicone oil and tetramethyl orthosilicate; the phosphorus source compound comprises one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus pentoxide and phosphoric acid.
8. The method of claim 5, wherein the copper-containing compound comprises one or more of: copper oxide, copper fluoride, copper nitrate, copper sulfate, copper chloride, basic copper carbonate, copper tartrate, copper acetylacetonate, copper acetate, and copper gluconate.
9. The preparation method according to claim 5, wherein the green sheet is subjected to high-temperature sintering to obtain a copper ion-doped NASICON type sodium ion ceramic electrolyte, comprising:
and (3) insulating the green sheet at 1000-1200 ℃ for 5-24 h, and sintering at high temperature to obtain the copper ion doped NASICON type sodium ion ceramic electrolyte.
10. An all-solid-state sodium metal battery comprising the NASICON-type sodium ion ceramic electrolyte of any one of claims 1-4.
CN202111556399.8A 2021-12-17 2021-12-17 NASICON type sodium ion ceramic electrolyte and preparation method thereof Pending CN114243097A (en)

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