CN115504770A - Transition metal ion and Nd 3+ Co-doped solid electrolyte ceramic material and preparation method thereof - Google Patents
Transition metal ion and Nd 3+ Co-doped solid electrolyte ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material of the formula I Na 1.67 Li 0.33 Al 10.67 O 17 On the basis of (1), introducing transition metal ions M and Nd 3+ (ii) a M is Mn 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ One of the ions introduced in an amount of Al in terms of a molar ratio 3+ ∶M＝50～150∶1；Nd 3+ Is introduced in a molar ratio of Al 3+ ∶Nd 3+ = 150-350: 1; m ion and Nd 3+ Doped into ceramicCeramic lattice substituted for Al 3+ ，Nd 3+ Also NdAlO 3 In the form of crystalline phases. In addition, a preparation method of the solid electrolyte ceramic material is also disclosed. The invention introduces Li + Stabilizing beta' -Al 2 O 3 On the basis of phase structure, doping transition metal ions M to reduce the sintering temperature and reduce Na + Volatilize while inhibiting beta' -Al 2 O 3 Crystal phase orientation beta-Al 2 O 3 Transformation of a crystalline phase; by Nd 3+ The doping of the electrolyte enables the material to have less defects and high density, thereby enhancing the electrical property of the solid electrolyte and further promoting the progress and development of the production technology of the sodium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of solid electrolyte ceramic materials, in particular to a high-Na sintered ceramic material sintered at a high temperature of more than 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 operating cost, easy maintenance, no environmental pollution, long service life and the like, is particularly suitable for being used as an energy storage battery for peak clipping and valley filling, and is commercially available for 30 years in 1992.
Na-β"(β)-Al 2 O 3 Not only the electrolyte material of the sodium-sulfur battery, but also the selective permeable membrane of the sodium-sulfur battery, is an important component of a sodium-sulfur battery, and the performance of the battery depends on the solid electrolyte Na-beta- (beta) -Al of the battery to a great extent 2 O 3 Thus, na-beta- (. Beta. -Al) 2 O 3 The preparation and performance research of electrolytes are also becoming increasingly important research areas.
Traditional synthesis of Na-beta' (beta) -Al 2 O 3 The main method is to mix high-purity alpha-Al 2 O 3 、Na 2 CO 3 And a small amount of a dopant such as MgO or Li 2 O, etc. and sintering at a high temperature of more than 1600 ℃. During the high temperature sintering process, the following problems tend to exist: one is Na + Is easy to volatilize, so that Na-beta' (beta) -Al is easily volatilized 2 O 3 The solid electrolyte deviates from the target composition, resulting in reduced performance; second is in Na 2 O-Al 2 O 3 beta-Al often exists in the system at the same time 2 O 3 And beta' -Al 2 O 3 Two crystalline phases, beta' -Al 2 O 3 The electrical conductivity of the phase is beta-Al 2 O 3 About 10 times of phase, but during high temperature sintering, beta' -Al 2 O 3 Phase orientation of beta-Al 2 O 3 Phase transitions, resulting in reduced performance; and thirdly, in the high-temperature sintering process, crystal grains in the electrolyte are easy to grow, so that the generated 'double structure' can reduce the ionic conductivity of the electrolyte and influence the service life of the sodium-sulfur battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material with introduction of Li + Stabilization of beta' -Al 2 O 3 On the basis of phase structure, transition metal ions are doped into the solid electrolyte, which is favorable for reducing the sintering temperature to reduce Na + While volatilizing, inhibiting beta' -Al 2 O 3 Crystal phase orientation beta-Al 2 O 3 The transformation of the crystal phase increases beta' -Al 2 O 3 Phase content; by Nd 3+ The doping of the material ensures that the material has less defects and high density, thereby enhancing Na-beta- (beta) -Al 2 O 3 The electrical properties of the solid electrolyte further promote the progress and development of the production technology of the sodium-sulfur battery. Another object of the present invention is to provide the above-mentioned transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 A method for preparing solid electrolyte ceramic and a product prepared by the method.
The purpose of the invention is realized by the following technical scheme:
the invention provides a transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material of the formula I Na 1.67 Li 0.33 Al 10.67 O 17 On the basis of (2), introducing a transition metalIons M and Nd 3+ (ii) a M is Mn 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ One of the ions introduced in an amount of Al in terms of a molar ratio 3+ ∶M＝50～150∶1；Nd 3+ Is introduced in a molar ratio of Al 3+ ∶Nd 3+ = 150-350: 1; m ion and Nd 3+ Doping into ceramic lattice to replace Al 3+ ，Nd 3+ Also NdAlO 3 In the form of a crystalline phase.
In the scheme, the volume density of the solid electrolyte ceramic material is more than 3.19g/cm 3 And an electrical conductivity at 300 ℃ of more than 0.08 S.cm -1 The electric conductivity activation energy is less than or equal to 0.1031eV.
The other purpose of the invention is realized by the following technical scheme:
the invention provides the transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material comprises the following steps:
(1) Preparation of buried burning material
alpha-Al is added 2 O 3 And Na 2 CO 3 According to the chemical formula Na 2 Al 10.67 O 17 Mixing materials, and performing ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; the material obtained after ball milling is calcined after being dried, screened and pressed into shape; grinding and sieving the calcined material to obtain a buried sintering material;
(2) Preparation of presynthesized precursor powder
Taking an aluminum source, a sodium source, a lithium source, a neodymium source and a transition metal ion M source as raw materials, wherein the aluminum source and the lithium source are according to a chemical formula I Na 1.67 Li 0.33 Al 10.67 O 17 The dosage of the sodium source is 8 to 12 percent more than the amount of the sodium source in the formula I, and the dosage of the transition metal ion M source is Al according to the molar ratio 3+ M = 50-150: 1, the dosage of the neodymium source is Al according to the molar ratio 3+ ∶Nd 3+ = 150-350: 1; then, carrying out primary ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; drying, sieving and pressing the material obtained after ball millingCalcining after molding; 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 material obtained after ball milling to obtain a treated material; putting the treated material into a die for compression molding, then performing cold isostatic pressing, and then performing binder removal heat treatment to obtain a pre-sintered part; and then, placing the pre-sintered part in a burying material for burying to obtain the solid electrolyte ceramic material.
Further, the preparation method of the present invention comprises alpha-Al in the step (1) 2 O 3 And Na 2 CO 3 The purity of (A) is not lower than 99.2%; the purity of the raw material in the step (2) is not less than 99.9 percent, 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 2 C 2 O 4 The lithium source is Li 2 CO 3 Or Li 2 C 2 O 4 Nd as the source of neodymium 2 O 3 (ii) a In the transition metal ion M source, the manganese source is MnCO 3 The cobalt source is CoO or 2CoCO 3 ·3Co(OH) 2 ·H 2 The O and nickel source is NiO or NiCO 3 ·2Ni(OH) 2 ·4H 2 The O and zinc source is ZnO or Zn 2 (OH) 2 CO 3 The copper source is CuO or CuCO 3 ·Cu(OH) 2 。
Further, the ball milling treatment in the step (1) of the preparation method of the invention is ball milling for more than 12 hours according to the ratio of balls to materials to absolute ethyl alcohol = 4: 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 ratio of balls to materials to absolute ethyl alcohol = 4: 1-3.
Furthermore, the preparation method of the invention has the advantages that the compression molding pressure of the step (1) and the step (2) is 4-6 Mpa, and the temperature is raised to 1100-1150 ℃ at the rate of 5 ℃/min for calcination treatment.
Furthermore, in the preparation method of the present invention, the binder used for granulation in step (3) is polyvinyl butyral or polyvinyl alcohol, and the amount of the polyvinyl butyral or polyvinyl alcohol is 3 to 7wt% of the material.
Further, in the step (3) of the preparation method, the mixture is pressed and molded under 6-8 Mpa; the pressure of cold isostatic pressing is 200-300 MPa, and the pressure maintaining time is at least 90s; the temperature of the glue discharging heat treatment is raised to 630-650 ℃ at 1 ℃/min.
Further, the temperature of the embedding burning treatment in the step (3) of the preparation method is raised to 1560-1640 ℃ at 5 ℃/min.
Using the above transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The product prepared by the preparation method of the solid electrolyte ceramic material.
The invention has the following beneficial effects:
(1) The invention adopts the following three measures in the process of preparing the solid electrolyte ceramic material: (a) Introducing excessive sodium source during batching to compensate Na in the high-temperature sintering process + Loss of (d); (b) Adopts sodium-containing buried burning material to carry out buried burning, and reduces Na in the high-temperature sintering process to a certain extent + The volatilization loss of (2); (c) In the introduction of Li + As beta' -Al 2 O 3 At the same time of phase crystal stabilizer, doped transition metal ion M and partial Nd 3+ Into ceramic lattice to replace Al 3+ Part of Nd 3+ With NdAlO 3 In the form of crystalline phases, all with stable beta' -Al 2 O 3 The effect of the phase is to reduce beta' -Al 2 O 3 Oppositely directed beta-Al 2 O 3 Phase inversion. The three measures enable the prepared solid electrolyte ceramic material to be beta' -Al 2 O 3 The phase content is high.
(2) The invention introduces Li + Stabilization of beta' -Al 2 O 3 Based on the phase structure, the rare earth oxide Nd 2 O 3 And oxides or salts of transition metals (e.g., manganese, cobalt, nickel, zinc, copper) are added to the solid electrolyte. Doped partial Nd 3+ With NdAlO 3 The crystal phase exists in the form of inhibiting the growth of crystal boundary and inhibiting the abnormal growth of crystal grainsSo that the ceramic crystal grains are finer and more uniform; on the other hand, the method can reduce fracture defects and accelerate densification, so that the material has less defects and high density (the average volume density is more than 3.19 g/cm) 3 ). The doping of transition metal ions can reduce the sintering temperature and reduce Na + Volatilizing to increase beta' -Al at high temp 2 O 3 Stability of the phases. Under the synergistic effect of the two, na-beta- (beta) -Al is finally enhanced 2 O 3 Properties of the solid electrolyte.
(3) The solid electrolyte ceramic material prepared by the invention is prepared from beta' -Al 2 O 3 High phase content, fine and uniform crystal grains and good compactness, so that the electrical property of the ceramic material is good, and the electrical conductivity of the ceramic material is more than 0.08S-cm at 300 DEG C -1 The electric conductivity activation energy is less than or equal to 0.1031eV.
(4) The preparation method of the invention does not need expensive equipment, has simple process and easy operation, easily controlled influence factors, repeatedly usable used buried sintering material and low production cost, and is beneficial to popularization and application.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
fig. 1 is an XRD spectrum of a solid electrolyte ceramic material prepared by an example of the present invention;
FIG. 2 is a SEM image (a: 5000 times; b:1000 times) of a solid electrolyte ceramic material prepared according to an embodiment of the present invention;
fig. 3 is an ac impedance spectrum of a solid electrolyte ceramic material prepared by an example of the present invention.
Detailed Description
The first embodiment is as follows:
this example shows transition metal ions and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material comprises the following steps:
(1) Preparation of buried burning material
alpha-Al with the purity of 99.31 percent and the fineness of 325 meshes 2 O 3 And Na with a purity of 99.28% 2 CO 3 According to the chemical formula Na 2 Al 10.67 O 17 Mixing materials, and performing ball milling treatment for 12 hours by using absolute ethyl alcohol as a ball milling medium according to the ratio of balls to materials to absolute ethyl alcohol = 4: 1: 1.2; drying the ball-milled material, sieving with a 60-mesh sieve, pressing under 4Mpa, heating to 1100 deg.C at 5 deg.C/min, calcining, and keeping the temperature for 2h; grinding the calcined material, and sieving with a 60-mesh sieve to obtain a buried calcined material;
(2) Preparation of presynthesized precursor powder
alpha-Al with the purity of 99.9 percent 2 O 3 (fineness 325 mesh) anhydrous Na 2 CO 3 、Li 2 CO 3 、Nd 2 O 3 And CoO as raw material, wherein alpha-Al 2 O 3 、Na 2 CO 3 、Li 2 CO 3 、Nd 2 O 3 And the dosage of CoO is respectively as follows: 100g, 17.90g, 2.2410g, 1.2177g, 0.7675; then, carrying out primary ball milling treatment for 12h by using absolute ethyl alcohol as a ball milling medium according to the ratio of balls to materials to absolute ethyl alcohol = 4: 1: 2; drying the ball-milled material, sieving with a 60-mesh sieve, pressing under 4Mpa, heating to 1100 deg.C at 5 deg.C/min, calcining, and keeping the temperature 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
Carrying out secondary ball milling treatment (the same as the primary ball milling treatment) on the pre-synthesized precursor powder, drying, grinding, sieving with an 80-mesh sieve, granulating (adding 2wt% of polyvinyl butyral absolute ethanol solution as a binder, wherein the polyvinyl butyral amount is 5wt% of the material), and ageing for 24 hours to obtain a treated material; putting 4.5g of the processing material into a mold, pressing under 6MPa to prepare a wafer with the thickness of 1.5mm and the diameter of 13mm, putting the wafer into a rubber glove, vacuumizing, and maintaining the pressure in a cold isostatic press under 200MPa for 90s; heating to 650 ℃ at the speed of 1 ℃/min for glue discharging treatment, preserving heat for 4h, and cooling along with a furnace to obtain a pre-sintered part; then, the pre-sintered piece is placed in a buried sintering material, the temperature is raised to 1600 ℃ at the speed of 5 ℃/min for buried sintering treatment, the temperature is kept for 30min, and the solid electrolyte ceramic material is prepared after furnace cooling.
Example two:
this example shows transition metal ions and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is different from the first embodiment in that:
in the step (2) of this example, the Al source and the M source are Al (OH) having a purity of 99.9%, respectively 3 And ZnO; in step (2), al (OH) 3 、Na 2 CO 3 、Li 2 CO 3 、Nd 2 O 3 And the dosage of ZnO is respectively as follows: 76.5006g, 19.53g, 2.2410g, 1.8g, 0.8330g; in the step (3), the temperature of the burying treatment is 1620 ℃.
Example three:
this example shows transition metal ions and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is different from the first embodiment in that:
in the step (2) of this example, al (OH) with a purity of 99.9% as an aluminum source 3 (ii) a In step (2), al (OH) 3 、Na 2 CO 3 、Li 2 CO 3 、Nd 2 O 3 And the dosage of CoO is respectively as follows: 76.5006g, 19.53g, 2.2410g, 1.1g, 1.2200g; in the step (3), the temperature of the burying and burning treatment is 1580 ℃.
Transition metal ions and Nd prepared by the embodiment of the invention 3+ Codoped Na-beta (beta') -Al 2 O 3 The XRD crystal phase spectrum of the solid electrolyte ceramic material is shown in figure 1, and the main crystal phase of the prepared ceramic material is beta' -Al 2 O 3 Containing a small amount of beta-Al 2 O 3 Phase sum NdAlO 3 Phase (1); due to M ion and Nd 3+ Into crystal lattice to replace Al 3+ The main crystal phase peak is shifted to the left. The scanning electron microscope image of the ceramic material is shown in fig. 2, and the ceramic material has a compact structure and small porosity.
And (3) performance testing:
alternating current impedance mapping and conductivity testing: by using an AC impedance method, an electrochemical workstation (AC amplitude) of DH7000 type manufactured by Donghua, china was usedIn the range of 10 -1 Hz-10 6 Hz, alternating current voltage of 20 mV) at a temperature of 300 ℃. The Na of the material was obtained by calculation + Conductivity: σ = h/(S · R), where σ is the conductivity, S · cm -1 (ii) a h is sample thickness, cm; s is the area of the sample covered with silver, cm 2 (ii) a R is the sample ac impedance value, Ω. The measured ac impedance profile is shown in fig. 3.
Conductivity activation energy calculation: using the conductivity σ of the sample, arrhenius formula σ T = Ae -Ea/(R·T) Logarithm is taken at two sides of the equation to obtain ln sigma T = lnA-Ea · R -1 T -1 Obtaining the slope of a graph by software fitting, wherein the slope is the activation energy value, and A is a characteristic constant; r is a molar gas constant; ea is the conductivity activation energy, and the unit is eV; t is the thermodynamic temperature in K.
Through the AC impedance spectrum and through relevant calculation, the conductivity and the conductivity activation energy of the ceramic material of the embodiment of the invention are shown in the table 1.
TABLE 1 conductivity and conductivity activation energy of ceramic materials of examples of the invention
Claims (10)
1. Transition metal ion and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The solid electrolyte ceramic material is characterized in that: in the formula I Na 1.67 Li 0.33 Al 10.67 O 17 On the basis of (1), introducing transition metal ions M and Nd 3+ (ii) a M is Mn 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ One of the ions introduced in an amount of Al in terms of a molar ratio 3+ ∶M＝50～150∶1；Nd 3+ Is introduced in a molar ratio of Al 3+ ∶Nd 3+ = 150-350: 1; m ion and Nd 3+ Doping into ceramic lattice to replace Al 3+ ，Nd 3+ Also NdAlO 3 In the form of a crystalline phase.
2. The transition metal ion of claim 1 with Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The solid electrolyte ceramic material is characterized in that: the volume density of the solid electrolyte ceramic material is more than 3.19g/cm 3 And an electrical conductivity at 300 ℃ of more than 0.08 S.cm -1 The electric conductivity activation energy is less than or equal to 0.1031eV.
3. The transition metal ion according to claim 1 or 2 and Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps:
(1) Preparation of buried burning material
alpha-Al is added 2 O 3 And Na 2 CO 3 According to the chemical formula Na 2 Al 10.67 O 17 Mixing materials, and performing ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; the material obtained after ball milling is calcined after being dried, screened and pressed into shape; grinding and sieving the calcined material to obtain a buried sintering material;
(2) Preparation of presynthesized precursor powder
Taking an aluminum source, a sodium source, a lithium source, a neodymium source and a transition metal ion M source as raw materials, wherein the aluminum source and the lithium source are according to a chemical formula I Na 1.67 Li 0.33 Al 10.67 O 17 The dosage of the sodium source is 8 to 12 percent more than the amount of the sodium source in the formula I, and the dosage of the transition metal ion M source is Al according to the molar ratio 3+ M = 50-150: 1, the dosage of the neodymium source is Al according to the molar ratio 3+ ∶Nd 3+ = 150-350: 1; then, carrying out primary ball milling treatment by taking absolute ethyl alcohol as a ball milling medium; the material obtained after ball milling is calcined after being dried, screened and pressed into shape; 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 material obtained after ball milling to obtain a treated material; putting the treated material into a die for compression molding, then performing cold isostatic pressing, and then performing binder removal heat treatment to obtain a pre-sintered part; and then, placing the pre-sintered piece into a burying material for burying, thus obtaining the solid electrolyte ceramic material.
4. Transition metal ions with Nd according to claim 3 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps: alpha-Al in the step (1) 2 O 3 And Na 2 CO 3 The purity of the product is not lower than 99.2%; the purity of the raw material in the step (2) is not lower than 99.9 percent, 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 2 C 2 O 4 The lithium source is Li 2 CO 3 Or Li 2 C 2 O 4 Nd as the source of neodymium 2 O 3 (ii) a In the transition metal ion M source, the manganese source is MnCO 3 The cobalt source is CoO or 2CoCO 3 ·3Co(OH) 2 ·H 2 The O and nickel source is NiO or NiCO 3 ·2Ni(OH) 2 ·4H 2 The O and zinc source is ZnO or Zn 2 (OH) 2 CO 3 The copper source is CuO or CuCO 3 ·Cu(OH) 2 。
5. The transition metal ion of claim 3 with Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps: the ball milling treatment in the step (1) is ball milling for more than 12 hours according to the ratio of balls to materials to absolute ethyl alcohol = 4: 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 ratio of balls to materials to absolute ethyl alcohol = 4: 1-3.
6. Transition metal ions with Nd according to claim 3 3+ Codoped Na-beta (beta') -Al 2 O 3 Solid electrolyte potteryThe preparation method of the porcelain material is characterized by comprising the following steps: the compression molding pressure of the step (1) and the step (2) is 4-6 Mpa, and the temperature is raised to 1100-1150 ℃ at the rate of 5 ℃/min for calcination treatment.
7. The transition metal ion of claim 3 with Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized in that the adhesive 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 3-7 wt% of the material.
8. The transition metal ion of claim 3 with Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps: in the step (3), the mixture is pressed and molded under 6-8 Mpa; the pressure of cold isostatic pressing is 200-300 MPa, and the pressure maintaining time is at least 90s; the temperature of the glue discharging heat treatment is raised to 630-650 ℃ at 1 ℃/min.
9. Transition metal ions with Nd according to claim 3 3+ Codoped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps: the temperature of the embedding burning treatment in the step (3) is raised to 1560-1640 ℃ at 5 ℃/min.
10. Use of a transition metal ion according to any one of claims 3 to 9 with Nd 3+ Codoped Na-beta (beta') -Al 2 O 3 The product is prepared by the preparation method of the solid electrolyte ceramic material.
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