CN115417660B - Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof - Google Patents
Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses Eu 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material with a chemical formula of Na 1.67 Li 0.33 Al 10.67‑x Eu x O 17 Wherein x=0.0013 to 0.003; eu (Eu) 3+ Doped into the ceramic lattice to replace Al 3+ . In addition, a preparation method of the solid electrolyte ceramic material is also disclosed. The invention introduces Li + Stabilizing beta' -Al 2 O 3 Based on the phase structure, eu is added 2 O 3 Doped into solid electrolyte, not only can reduce sintering temperature to reduce Na + Is volatilized; at the same time, eu 3+ Doped into the ceramic lattice to replace Al 3+ Inhibit beta' -Al 2 O 3 beta-Al with crystal phase orientation 2 O 3 Transformation of the crystalline phase to give beta' -Al 2 O 3 Pure phase, thereby enhancing Na-beta "(beta) -Al 2 O 3 The electrical property of the solid electrolyte is further beneficial to promoting the progress and development of sodium-sulfur battery production technology.
Description
Technical Field
The invention relates to the technical field of solid electrolyte ceramic materials, in particular to a high-temperature sintering method with high Na at 1550 DEG C + A solid electrolyte ceramic material with conductivity and a preparation method thereof.
Background
The sodium-sulfur battery has the advantages of high energy storage density, high efficiency, low operation cost, easier maintenance, no environmental pollution, long service life and the like, and is particularly suitable for being used as an energy storage battery for peak clipping and valley filling, and the commercial use has been 30 years before 1992.
Na-β"(β)-Al 2 O 3 Not only is the electrolyte material of the sodium-sulfur battery, but also the selective permeable membrane of the sodium-sulfur battery is an important component of the sodium-sulfur battery, and the performance of the battery is greatly dependent on the solid electrolyte Na-beta "(beta) -Al 2 O 3 Thus, na-beta "(beta) -Al 2 O 3 The preparation and performance research of electrolytes are also becoming important research fields.
Traditional synthesis of Na-beta (beta) -Al 2 O 3 The main method is to make high purity alpha-Al 2 O 3 、Na 2 CO 3 And small amounts of dopants such as MgO or Li 2 Mixing with O, and sintering at 1600 deg.C or higher. In the high temperature sintering process, there are often the following problems: first is Na + Is easy to volatilize, so that Na-beta (beta) -Al 2 O 3 The solid electrolyte deviates from the target composition, resulting in reduced performance; second is Na 2 O-Al 2 O 3 beta-Al is often simultaneously present in the system 2 O 3 And beta' -Al 2 O 3 Two crystalline phases, beta "-Al 2 O 3 The conductivity of the phase is beta-Al 2 O 3 About 10 times of the phase, but during high temperature sintering, beta "-Al 2 O 3 Easy phase orientation beta-Al 2 O 3 Phase transition, resulting in reduced performance; thirdly, in the high-temperature sintering process, crystal grains in the electrolyte are easy to grow up, so that the generated double structure not only can reduce the ionic conductivity of the electrolyte, but also can influence the service life of the sodium-sulfur battery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a Eu 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material, in which Li is introduced + Stabilizing beta' -Al 2 O 3 Based on the phase structure, rare earth oxide Eu 2 O 3 Doped into solid electrolyte to reduce Na in favor of lowering sintering temperature + Volatilized and volatilizedAt the same time inhibit beta' -Al 2 O 3 beta-Al with crystal phase orientation 2 O 3 Transformation of the crystalline phase to give beta' -Al 2 O 3 Pure phase, thereby enhancing Na-beta (beta) -Al 2 O 3 The electrical properties of the solid electrolyte further promote the progress and development of sodium-sulfur battery production technology. Another object of the present invention is to provide Eu as described above 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A method for preparing solid electrolyte ceramic and a product prepared by the method.
The aim of the invention is realized by the following technical scheme:
the Eu provided by the invention 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The chemical formula of the solid electrolyte ceramic material is shown as a chemical formula I: na (Na) 1.67 Li 0.33 Al 10.67-x Eu x O 17 Wherein x=0.0013 to 0.003; eu (Eu) 3+ Doped into the ceramic lattice to replace Al 3 + 。
In the scheme, the solid electrolyte ceramic material has the conductivity of more than 0.045S cm at 300 DEG C -1 The conductivity activation energy is less than 0.115eV.
The other object of the invention is achieved by the following technical scheme:
eu provided by the invention 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material comprises the following steps:
(1) Preparation of buried firing material
alpha-Al 2 O 3 And Na (Na) 2 CO 3 According to chemical formula Na 2 Al 10.67 O 17 Batching, and performing ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; drying, sieving, pressing and forming the materials obtained after ball milling, and calcining; grinding and sieving the calcined material to obtain a buried sintered material;
(2) Preparation of presynthesized precursor powders
The preparation method comprises the steps of preparing materials of an aluminum source, a sodium source, a lithium source and a europium source, wherein the aluminum source, the lithium source and the europium source are prepared according to a chemical formula I, and the dosage of the sodium source is 8-12% more than the dosage of the sodium source in the chemical formula I; then, absolute ethyl alcohol is used as a ball milling medium for carrying out ball milling treatment for the first time; drying, sieving, pressing and forming the materials obtained after ball milling, and calcining; grinding and sieving the calcined material to obtain pre-synthesized precursor powder;
(3) Preparation of solid electrolyte ceramics
Performing secondary ball milling treatment on the pre-synthesized precursor powder, and drying, grinding, sieving, granulating and ageing the materials obtained after ball milling to obtain treated materials; placing the treated material into a mould for compression molding, then carrying out cold isostatic pressing, and then carrying out glue discharging heat treatment to obtain a presintered piece; and then placing the presintered piece into a burn-in material for burn-in, thus obtaining the solid electrolyte ceramic material.
Further, the preparation method of the invention comprises the step (1) of alpha-Al 2 O 3 And Na (Na) 2 CO 3 The purity of (2) is not lower than 99.2%; the purity of the raw material in the step (2) is not lower than 99.9%, and the aluminum source is alpha-Al 2 O 3 Or Al (OH) 3 The sodium source is anhydrous Na 2 CO 3 Or Na (or) 2 C 2 O 4 The lithium source is Li 2 CO 3 Or Li (lithium) 2 C 2 O 4 Eu is the europium source 2 O 3 。
Further, the ball milling treatment in the step (1) of the preparation method is ball milling for more than 12 hours according to the ratio of ball to material to absolute ethyl alcohol=4:1:1-1.5; the primary ball milling treatment and the secondary ball milling treatment in the step (2) are the same, and ball milling is carried out for more than 12 hours according to the proportion of balls, materials and absolute ethyl alcohol=4:1:1-3.
Further, the compression molding pressure of the step (1) and the step (2) is 4-6 Mpa, and the calcining treatment is that the temperature is raised to 1100-1150 ℃ at 5 ℃/min.
Further, the binder used for granulation in the step (3) of the preparation method adopts polyvinyl butyral or polyvinyl alcohol, and the dosage of the polyvinyl butyral or the polyvinyl alcohol is 3-7wt% of the material.
Further, in the step (3), the preparation method of the invention is to press and shape under 6-8 Mpa; the pressure of the cold isostatic pressing is 200-300 MPa, and the pressure maintaining time is at least 90s; the temperature of the heat treatment of the adhesive discharge is raised to 630-650 ℃ at 1 ℃/min.
Further, the temperature of the burying treatment in the step (3) is raised to 1580-1640 ℃ at 5 ℃/min.
By using Eu as described above 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The product is prepared by the preparation method of the solid electrolyte ceramic material.
The invention has the following beneficial effects:
(1) In the process of preparing the solid electrolyte ceramic material, the following three measures are adopted: (a) Introducing excessive sodium source during the material mixing to compensate Na during high temperature sintering + Is a loss of (2); (b) The sodium-containing sintering material is adopted for sintering, so that Na in the high-temperature sintering process is reduced to a certain extent + Is a volatile loss of (2); (c) At the time of introducing Li + Doped Eu as a stabilizer for beta' phase crystal forms 3+ Into ceramic lattice to replace Al 3+ Further stabilize beta' -Al 2 O 3 Crystalline phase, inhibited beta' -Al 2 O 3 beta-Al with crystal phase orientation 2 O 3 Transformation of the crystalline phase. The three measures lead the prepared solid electrolyte ceramic material to be beta' -Al 2 O 3 Pure phase.
(2) The solid electrolyte ceramic material prepared by the invention is beta' -Al 2 O 3 Pure phase, thus the ceramic material has good electrical property, and the conductivity of the ceramic material is changed from undoped Eu at 300 DEG C 3+ 0.026S.cm -1 Lifting to more than 0.045S.cm -1 。
(3) The preparation method of the invention has the advantages of no need of expensive equipment, simple and easy operation of the process, easy control of influencing factors, repeated use of the used buried firing material, low production cost and contribution to popularization and application.
Drawings
The invention will be described in further detail with reference to examples and figures:
FIG. 1 is an XRD pattern of a solid electrolyte ceramic material prepared according to an embodiment of the present invention;
FIG. 2 is a SEM image (a: 10000 times; b:20000 times) of a solid electrolyte ceramic material according to an embodiment of the present invention;
FIG. 3 is an AC impedance spectrum of a solid electrolyte ceramic material prepared according to an embodiment of the present invention.
Detailed Description
Embodiment one:
eu of this embodiment 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material comprises the following steps:
(1) Preparation of buried firing material
alpha-Al with purity of 99.31% and fineness of 325 meshes is prepared 2 O 3 And Na with purity of 99.28% 2 CO 3 According to chemical formula Na 2 Al 10.67 O 17 Batching, and performing ball milling treatment for 12 hours by taking absolute ethyl alcohol as a ball milling medium according to the ratio of ball to material to absolute ethyl alcohol=4:1:1.2; drying the materials obtained after ball milling, sieving with a 60-mesh sieve, pressing and forming under 4Mpa, heating to 1100 ℃ at 5 ℃/min for calcining treatment, and preserving heat for 2h; grinding the calcined material, and sieving with a 60-mesh sieve to obtain a buried sintered material;
(2) Preparation of presynthesized precursor powders
In the form of anhydrous Na with purity of 99.9% 2 CO 3 、Li 2 CO 3 、Eu 2 O 3 And alpha-Al 2 O 3 (fineness of 325 mesh) as raw material, wherein Li 2 CO 3 、Eu 2 O 3 And alpha-Al 2 O 3 The dosage of (C) is according to the chemical formula Na 1.67 Li 0.33 Al 10.6677 Eu 0.0023 O 17 Proportioning Na 2 CO 3 The amount of (2) is 10% more than the amount of the catalyst in the chemical formula; then ball milling is carried out for 12 hours by taking absolute ethyl alcohol as a ball milling medium according to the ratio of ball to material to absolute ethyl alcohol=4:1:2; obtained after ball millingDrying the materials, sieving with a 60-mesh sieve, pressing and forming under 4Mpa, heating to 1100 ℃ at 5 ℃/min, calcining, and preserving heat for 2h; grinding the calcined material, and sieving with a 60-mesh sieve to obtain pre-synthesized precursor powder;
(3) Preparation of solid electrolyte ceramics
Performing secondary ball milling treatment (the same as the primary ball milling treatment) on the pre-synthesized precursor powder, drying, grinding, sieving with a 80-mesh sieve, granulating (adding an absolute ethanol solution of polyvinyl butyral with the concentration of 2wt% as a binder, wherein the dosage of the polyvinyl butyral is 5wt% of that of the material), and ageing for 24 hours to obtain a treated material; 4.5g of the treated material is put into a mould to be pressed into a circular sheet with the thickness of 1.5mm and the diameter of 13mm under the pressure of 6Mpa, then the circular sheet is put into rubber gloves, vacuumized and put into a cold isostatic press to be maintained for 90s under 200 Mpa; then heating to 650 ℃ at a speed of 1 ℃/min for glue discharging treatment, preserving heat for 4 hours, and cooling along with a furnace to obtain a presintered piece; then, the presintering piece is placed in a burn-in material, the temperature is raised to 1600 ℃ at 5 ℃/min for burn-in treatment, the temperature is kept for 30min, and the solid electrolyte ceramic material is obtained after cooling along with a furnace.
Embodiment two:
eu of this embodiment 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is different from the embodiment in that:
in the step (2) of this example, the aluminum source was Al (OH) having a purity of 99.9% 3 The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula in the step (2) is Na 1.67 Li 0.33 Al 10.667 Eu 0.003 O 17 ，Na 2 CO 3 The amount of (2) is 10% more than the amount of the catalyst in the chemical formula; the temperature of the burying treatment in the step (3) is 1620 ℃.
Embodiment III:
eu of this embodiment 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is different from the embodiment in that:
in the step (2) of the present embodiment, the aluminum source is Al with a purity of 99.9%(OH) 3 The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula in the step (2) is Na 1.67 Li 0.33 Al 10.668 Eu 0.002 O 17 ，Na 2 CO 3 The amount of (2) is 8% more than the amount of the catalyst in the chemical formula; the burying treatment temperature in the step (3) is 1590 ℃.
Eu prepared by the embodiment of the invention 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The XRD crystal phase diagram of the solid electrolyte ceramic material is shown in figure 1, and the prepared ceramic material is beta' -Al 2 O 3 Pure phase; due to Eu 3+ Into lattice to replace Al 3+ The main phase peak is shifted to the left. The scanning electron microscope image is shown in figure 2, and the ceramic material has a compact structure and small porosity.
Performance test:
ac impedance profile and conductivity test: an ac impedance method was used, and a DH7000 electrochemical workstation (ac amplitude range: 10) -1 Hz-10 6 Hz, ac voltage of 20 mV) test the ac impedance profile of the ceramic sample at a temperature of 300 ℃. By calculation of Na of the material + Conductivity: σ=h/(s·r), where σ is the conductivity, s·cm -1 The method comprises the steps of carrying out a first treatment on the surface of the h is the sample thickness, cm; s is the silver-coated area of the sample, cm 2 The method comprises the steps of carrying out a first treatment on the surface of the R is the alternating current impedance value of the sample, and omega. The ac impedance spectrum is shown in fig. 3.
Conductivity activation energy calculation: arrnhenius formula σt=ae, using the conductivity σ of the sample -Ea/(R·T) Taking the logarithm of both sides of the equation yields lnσt= lnA-ea·r -1 T -1 Obtaining the slope of a graph line through software fitting, wherein the slope is an activation energy value, and A is a characteristic constant; r is molar gas constant; ea is the conductivity activation energy in eV; t is the thermodynamic temperature in K.
The conductivity and the conductivity activation energy of the ceramic material of the embodiment of the invention are shown in table 1 through the related calculation by the alternating current impedance spectrum.
TABLE 1 conductivity and conductivity activation energy of ceramic materials of examples of the invention
Claims (5)
1. Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A solid electrolyte ceramic material characterized in that: the chemical formula of the solid electrolyte ceramic material is shown as a chemical formula I: na (Na) 1.67 Li 0.33 Al 10.67-x Eu x O 17 Wherein x=0.0013 to 0.003; eu (Eu) 3+ Doped into the ceramic lattice to replace Al 3+ The method comprises the steps of carrying out a first treatment on the surface of the The solid electrolyte ceramic material has a conductivity of > 0.045S cm at 300 DEG C -1 Conductivity activation energy < 0.115 eV; the preparation method of the electrolyte ceramic material comprises the following steps:
(1) Preparation of buried firing material
alpha-Al 2 O 3 And Na (Na) 2 CO 3 According to chemical formula Na 2 Al 10.67 O 17 Batching, and performing ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; drying, sieving, pressing and forming under 4-6 MPa, heating to 1100-1150 deg.C at 5 deg.C/min, and calcining; grinding and sieving the calcined material to obtain a buried sintered material;
(2) Preparation of presynthesized precursor powders
The preparation method comprises the steps of preparing materials of an aluminum source, a sodium source, a lithium source and a europium source, wherein the aluminum source, the lithium source and the europium source are prepared according to a chemical formula I, and the dosage of the sodium source is 8-12% more than the dosage of the sodium source in the chemical formula I; then, absolute ethyl alcohol is used as a ball milling medium for carrying out ball milling treatment for the first time; drying, sieving, pressing and forming under 4-6 MPa, heating to 1100-1150 deg.C at 5 deg.C/min, and calcining; grinding and sieving the calcined material to obtain pre-synthesized precursor powder;
(3) Preparation of solid electrolyte ceramics
Performing secondary ball milling treatment on the pre-synthesized precursor powder, and drying, grinding, sieving, granulating and ageing the materials obtained after ball milling to obtain treated materials; placing the treated material into a mould for compression molding, then carrying out cold isostatic pressing, and then carrying out glue discharging heat treatment to obtain a presintered piece; and then placing the presintered piece into a burn-in material, and heating to 1580-1640 ℃ at a speed of 5 ℃/min for burn-in, thus obtaining the solid electrolyte ceramic material.
2. The Eu of claim 1 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A solid electrolyte ceramic material characterized in that: alpha-Al in the step (1) 2 O 3 And Na (Na) 2 CO 3 The purity of (2) is not lower than 99.2%; the purity of the raw material in the step (2) is not lower than 99.9%, and the aluminum source is alpha-Al 2 O 3 Or Al (OH) 3 The sodium source is anhydrous Na 2 CO 3 Or Na (or) 2 C 2 O 4 The lithium source is Li 2 CO 3 Or Li (lithium) 2 C 2 O 4 Eu is the europium source 2 O 3 。
3. The Eu of claim 1 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A solid electrolyte ceramic material characterized in that: the ball milling treatment in the step (1) is carried out according to the ratio of ball to material to absolute ethyl alcohol=4:1:1-1.5, and the ball milling is carried out by more than 12 and h; the primary ball milling treatment in the step (2) is the same as the secondary ball milling treatment in the step (3), and the ball milling is performed according to the proportion of ball to material to absolute ethyl alcohol=4:1:1-3, and the ball milling is performed by more than 12 h.
4. The Eu of claim 1 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A solid electrolyte ceramic material characterized in that: the binder used for granulation in the step (3) adopts polyvinyl butyral or polyvinyl alcohol, and the dosage of the polyvinyl butyral or the polyvinyl alcohol is 3-7wt% of the material.
5. The Eu of claim 1 2 O 3 Doped Na-beta (beta') -Al 2 O 3 A solid electrolyte ceramic material characterized in that: in the step (3), the mixture is pressed and molded under the pressure of 6-8 MPa; the pressure of the cold isostatic pressing is 200-300 MPa, and the pressure maintaining time is at least 90s; the temperature of the heat treatment of the adhesive discharge is raised to 630-650 ℃ at 1 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211112360.1A CN115417660B (en) | 2022-09-13 | 2022-09-13 | Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211112360.1A CN115417660B (en) | 2022-09-13 | 2022-09-13 | Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof |
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