CN115417667A - Nd (Nd) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof - Google Patents
Nd (Nd) 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 an Nd 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material of formula Na 1.67 Li 0.33 Al 10.67‑x Nd x O 17 Wherein x = 0.003-0.005; nd (neodymium) 3+ Doping into ceramic lattice to replace Al 3+ ，Nd 3+ Also NdAlO 3 In the form of a crystalline phase. In addition, a preparation method of the solid electrolyte ceramic material is also disclosed. The invention introduces Li + Stabilization of beta' -Al 2 O 3 Based on the phase structure, nd 2 O 3 By doping into solid electrolyte, not only the sintering temperature can be reduced to reduce Na + Volatilizing; simultaneously, partially doped Nd 3+ Into ceramic lattice to replace Al 3+ To further stabilize beta ″‑Al 2 O 3 Phase, also partially doped Nd 3+ With NdAlO 3 The crystal phase exists in a form, which can prevent the abnormal growth of ceramic grains and make the ceramic more compact, thereby effectively 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 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 a sodium-sulfur battery but also the selectively permeable membrane of the sodium-sulfur battery are important components of the sodium-sulfur battery, and the performance of the battery depends greatly 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 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 1600 ℃ or higher. 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 transformation, 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 provides an Nd 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material incorporating Li + Stabilization of beta' -Al 2 O 3 Based on the phase structure, the rare earth oxide Nd 2 O 3 Doped into solid electrolyte to reduce Na while lowering sintering temperature + Nd partially doped while volatilizing 3+ Into ceramic lattice to replace Al 3+ To further stabilize beta' -Al 2 O 3 Phase, partially doped Nd 3+ With NdAlO 3 The crystal phase is in a form that can prevent abnormal growth of ceramic grains and make the ceramic more compact, 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 Nd 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 purpose of the invention is realized by the following technical scheme:
the invention provides an Nd 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The solid electrolyte ceramic material has a chemical formula I: na (Na) 1.67 Li 0.33 Al 10.67-x Nd x O 17 Wherein x = 0.003-0.005; nd (neodymium) 3+ Doping into ceramic lattice to replace Al 3 + ，Nd 3+ Also NdAlO 3 In the form of a crystalline phase.
In the above-mentioned scheme, the first step of the method,the volume density of the solid electrolyte ceramic material is more than 3.17g/cm 3 The conductivity at 300 ℃ is more than or equal to 0.06 S.cm -1 The electric conductivity activation energy is less than or equal to 0.109eV.
The other purpose of the invention is realized by the following technical scheme:
the invention provides the Nd 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 the buried sinter
alpha-Al is reacted with 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, sieved and pressed into shape; grinding and sieving the calcined material to obtain a buried calcined material;
(2) Preparation of presynthesized precursor powder
Taking an aluminum source, a sodium source, a lithium source and a neodymium source as raw materials for mixing, wherein the aluminum source, the lithium source and the neodymium source are mixed 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, 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 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 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 Nd 2 O 3 。
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 compression molding pressure of the step (1) and the step (2) in the preparation method is 4-6 Mpa, and the temperature is increased 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 treatment of the rubber discharge heat is to heat up to 630-650 ℃ at 1 ℃/min.
Further, the temperature of the burying burning treatment in the step (3) of the preparation method is increased to 1560-1640 ℃ at 5 ℃/min.
Using the above Nd 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 batching to compensate Na in the high-temperature sintering process + Loss of (d); (b) The sodium-containing burying material is adopted for burying, so that the high temperature is reduced to a certain extentNa in the sintering process + The volatilization loss of (2); (c) In the introduction of Li + As beta' -Al 2 O 3 Nd partially doped at the same time as phase crystal type stabilizer 3+ Into ceramic lattice to replace Al 3+ Further stabilizing beta' -Al 2 O 3 Phase, reduced by beta' -Al 2 O 3 Opposite phase beta-Al 2 O 3 Phase inversion. The three measures make the prepared solid electrolyte ceramic material beta' -Al 2 O 3 The phase content is high.
(2) The solid electrolyte ceramic material prepared by the invention is partially doped Nd 3+ With NdAlO 3 The existence of crystalline phase prevents the abnormal growth of ceramic grains, so that the ceramic grains are finer and more uniform, the ceramic is more compact, and the average volume density of the ceramic is more than 3.17g/cm 3 。
(3) The solid electrolyte ceramic material prepared by the invention is characterized in that 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 or equal to 0.06S-cm at 300 DEG C -1 The electric conductivity activation energy is less than or equal to 0.109eV.
(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 be described in further detail below with reference to examples and figures:
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: 10000 times; b:5000 times) of a solid electrolyte ceramic material prepared by an example 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:
nd in 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 burning material
alpha-Al with purity of 99.31% and 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
Anhydrous Na with purity of 99.9% 2 CO 3 、Li 2 CO 3 、Nd 2 O 3 And alpha-Al 2 O 3 (the fineness is 325 meshes) is taken as a raw material for mixing, wherein Li 2 CO 3 、Nd 2 O 3 And alpha-Al of 2 O 3 In an amount according to the formula Na 1.67 Li 0.33 Al 10.666 Nd 0.004 O 17 Mixing the materials with Na 2 CO 3 The amount of (A) is 10% more than the amount of the formula; then, carrying out primary ball milling treatment for 12 hours by taking 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 the treated material into a mold, pressing under 6Mpa to obtain a wafer with the thickness of 1.5mm and the diameter of 13mm, putting the wafer into a rubber glove, vacuumizing, and keeping 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.
The second embodiment:
this embodiment is an Nd 2 O 3 Doped 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 The chemical formula in the step (2) is Na 1.67 Li 0.33 Al 10.6655 Nd 0.0045 O 17 (ii) a In the step (3), the temperature of the burying treatment is 1620 ℃.
Example three:
this embodiment is an Nd 2 O 3 Doped 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 an Al source purity of 99.9% 3 (ii) a The chemical formula in the step (2) is Na 1.67 Li 0.33 Al 10.6665 Nd 0.0035 O 17 ，Na 2 CO 3 The amount of (A) is 8% more than the amount of the formula; the temperature of the burying burning treatment in the step (3) is 1580 ℃.
Nd prepared by the embodiment of the invention 2 O 3 Doped 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 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 Nd 3+ Into crystal lattice to replace Al 3+ The main crystal phase peak is shifted to the left. The scanning electron micrograph is shown in FIG. 2The ceramic material has a dense structure and a low porosity, and the average bulk density of the ceramic material is greater than 3.17g/cm 3 。
And (3) performance testing:
alternating current impedance mapping and conductivity testing: by using an AC impedance method, using a DH7000 type electrochemical workstation (AC amplitude range of 10) of Donghua, china -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 on 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. Nd (Nd) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The solid electrolyte ceramic material is 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 Nd x O 17 Wherein x = 0.003-0.005; nd (neodymium) 3+ Doping into ceramic lattice to replace Al 3+ ，Nd 3+ Also NdAlO 3 In the form of a crystalline phase.
2. The Nd according to claim 1 2 O 3 Doped 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 3.17g/cm 3 The conductivity at 300 ℃ is more than or equal to 0.06 S.cm -1 The electric conductivity activation energy is less than or equal to 0.109eV.
3. Nd according to claim 1 or 2 2 O 3 Doped 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 the buried sinter
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 and a neodymium source as raw materials for mixing, wherein the aluminum source, the lithium source and the neodymium source are mixed according to the 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, 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 part in a burying material for burying to obtain the solid electrolyte ceramic material.
4. Nd according to claim 3 2 O 3 Doped 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 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 Nd 2 O 3 。
5. The Nd according to claim 3 2 O 3 Doped 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 that the ball milling is carried out 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. The Nd according to claim 3 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic 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 calcination treatment is carried out by heating to 1100-1150 ℃ at the speed of 5 ℃/min.
7. Nd according to claim 3 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The preparation method of the solid electrolyte ceramic material is characterized by comprising the following steps: the adhesive used for granulating in the step (3) adopts polyvinyl butyral or polyvinyl alcohol, polyvinyl butyral or polyvinyl alcoholThe dosage of the vinyl alcohol is 3-7 wt% of the material.
8. The Nd according to claim 3 2 O 3 Doped 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. The Nd according to claim 3 2 O 3 Doped 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 Nd according to one of claims 3 to 9 2 O 3 Doped Na-beta (beta') -Al 2 O 3 The product prepared by the preparation method of the solid electrolyte ceramic material.
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| JPH03190058A (en) * | 1989-12-20 | 1991-08-20 | Hitachi Ltd | Solid electrolyte plate for na/s secondary battery, manufacture thereof, and na/s secondary battery using this plate |
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