CN101734911B - Preparation method of Na-beta''-Al2O3 solid electrolyte - Google Patents
Preparation method of Na-beta''-Al2O3 solid electrolyte Download PDFInfo
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- CN101734911B CN101734911B CN2009102644290A CN200910264429A CN101734911B CN 101734911 B CN101734911 B CN 101734911B CN 2009102644290 A CN2009102644290 A CN 2009102644290A CN 200910264429 A CN200910264429 A CN 200910264429A CN 101734911 B CN101734911 B CN 101734911B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910003155 β′′-Al2O3 Inorganic materials 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011240 wet gel Substances 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 150000001457 metallic cations Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- TWLBWHPWXLPSNU-UHFFFAOYSA-L [Na].[Cl-].[Cl-].[Ni++] Chemical compound [Na].[Cl-].[Cl-].[Ni++] TWLBWHPWXLPSNU-UHFFFAOYSA-L 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 229940001516 sodium nitrate Drugs 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a preparation method of a Na-beta''-Al2O3 solid electrolyte, comprising the following steps of: adding a stabilizer in a compound containing sodium, aluminium and magnesium or lithium as a raw material; preparing precursor powder; placing the prepared precursor powder into a microwave oven after being subjected to prilling and molding; and fast sintering to obtain the Na-beta''-Al2O3 electrolyte. The method not only has short reaction time and can furthest reduce the loss of Na2O and ensure the conductivity of the material, but also has low energy consumption and high temperature rate and can obtain a sample with higher compactness; and in addition, the Na-beta''-Al2O3 solid electrolyte prepared by the method shows excellent property and is suitable for being used as the solid electrolyte of a sodium-sulphur battery and a sodium-nickel chloride battery.
Description
Technical field
The present invention relates to a kind of preparation method of solid electrolyte material, particularly a kind of beta battery Na-β " Al that is applied to
2O
3The method of solid electrolyte.
Background technology
Because petroleum resources and other fossil energy is day by day exhausted, the at present development and utilization of the green energy resources such as wind energy and sun power in China just flourish, yet the energy storage technology of wind energy and sun power becomes its restraining factors that can not be applied to extensive generating at present.The extensive electric power energy storage technology that scientists is being developed is mainly secondary accumulator battery, as energy-storage battery, must satisfy a series of requirement: power density is high, energy density is high, cost is low, self-discharge rate is low, have extended cycle life and safety performance good etc.Current people to secondary battery research more be sodium-sulfur cell and the sodium nickelous chloride battery that is known as the beta battery.The diaphragm material that these two kinds of batteries are used is Na-β " Al
2O
3Solid electrolyte, the quality of its quality and performance is directly connected to performance and the working life of battery, and relies on greatly its preparation technology, is always paid attention to by the investigator.
Na-β " Al
2O
3The preparation method reaction sintering, spray-drying process, sol-gel method, microwave sintering method, partial synthesis method etc. are arranged a lot.Prior synthesizing method comprises synthetic and two processes of sintering.In traditional synthetic way, in order to obtain high fine and close Na-β " Al
2O
3Ionogen usually requires be higher than for a long time insulation under 1580 ℃ the condition, and high-temperature heat treatment can cause Na-β " Al for a long time
2O
3Middle Na
2A large amount of volatilizations of O, thus its ionic conductivity reduced.
Summary of the invention
The purpose of this invention is to provide a kind of sintering time that shortens solid electrolyte material, reduce Na
2O runs off, and improves a kind of Na-β " Al of density and specific conductivity
2O
3Method for preparing solid electrolyte.The standby solid electrolyte material of this legal system demonstrates excellent performance.
The object of the invention technical scheme is: take the compound that contains sodium, aluminium, magnesium or lithium as raw material, add stablizer, the preparation precursor powder after granulation, moulding, is put into microwave oven with the precursor powder that makes, and Fast Sintering obtains Na-β " Al
2O
3Ionogen.
Concrete technical scheme of the present invention is: a kind of Na-β " Al
2O
3Method for preparing solid electrolyte, its concrete steps are: (1) gets the salt that contains aluminium, sodium and magnesium, be dissolved in the solvent, be Na according to target product
1+xO Al
11-xMg
xO
16In the stoichiometric ratio weighing of metallic element be mixed to get mixing solutions, 0.45＜x＜1.0 wherein; Perhaps getting the salt that contains aluminium, sodium and lithium, be dissolved in the solvent, is Na according to target product
1+2yO Al
11-yLi
yO
16In the stoichiometric ratio weighing of metallic element be mixed to get mixing solutions, 0.2＜y＜0.5 wherein; (2) in above-mentioned mixing solutions, add macromolecular compound and dispersion agent, heating, stirring, reaction obtains wet gel; (3) with the wet gel oven dry that obtains, obtain xerogel; (4) with the xerogel calcining, obtain precursor powder; (5) with after the presoma granulation that obtains, the moulding, put into microwave oven, adopt the mode of Fractional Heat-treatment, namely be warming up to 1350～1450 ℃, be incubated after 10～60 minutes, continue to be warming up to 1500-1550 ℃, be incubated 3～60 minutes, and then obtain Na-β " Al through quench treatment
2O
3Ceramic electrolyte.
Wherein preferred described salt is nitrate, carbonate, chlorate, acetate, Citrate trianion, oxalate, formate or lactic acid salt.Preferred described macromolecular compound is citric acid, oxalic acid or tartrate; Dispersion agent is polyvinyl alcohol or polyoxyethylene glycol.The mol ratio of the add-on of described macromolecular compound and all metallic cation sums is 0.5～2: 1; The add-on of dispersion agent and the mol ratio of macromolecular compound are 0.5～2: 2.
The thermostatically heating temperature is 60-100 ℃ in the preferred steps (2), reacts 6～30 hours; Bake out temperature is 200～300 ℃ in the step (3).
Adopt a step sintering process in the above-mentioned steps (4), namely controlling temperature rise rate is 100～200 ℃/hour, and being warming up to sintering temperature is 800～1400 ℃, and soaking time is 1～5 hour.Sintering process adopts the step sintering method in the step (5), the speed of controlling first 10～15 ℃/min is warming up to 1350～1450 ℃, is incubated after 10～60 minutes, continues to be warming up to 1500-1550 ℃ with the speed of 10～15 ℃/min, be incubated 3～60 minutes, then quench.The output rating of preferred microwave oven is 3kW～6kW; Quench treatment is 1400～1500 ℃ of quenchings, is incubated 15-60 minute at every turn, and quenching times is one or many.
Preferred above-mentioned solvent is deionized water, and the add-on of solvent is as the criterion for dissolving above-mentioned salt.
The prepared ionogen of the present invention is applicable to the beta battery, and described beta battery is sodium-sulfur cell or sodium nickelous chloride battery.
Wherein the above-mentioned method for preparing presoma also can be solvent combustion method and direct solid-phase ball milling hybrid system: the method that the solvent combustion method prepares precursor powder is the salt with aluminium, sodium and magnesium (or lithium), be dissolved in respectively in the distilled water, be mixed to get mixing solutions according to the stoichiometric ratio weighing of the metallic element in the target product; Add combustible solvent (ethanol, Padil, urea and polyoxyethylene glycol etc.), the mol ratio of the add-on of combustible solvent and all metallic cation sums is 1～2: 1,60～100 ℃ of thermostatically heating, stirring, with the solution evaporate to dryness, continuous heating makes its burning, obtains loose powdered, with dehydrated alcohol as medium with powder ball milling 2～10 hours, the oven dry, sieving obtains powder, and 800～1200 ℃ of calcinings, soaking time obtained precursor powder in 2～4 hours with powder.The method that solid phase method prepares precursor powder is for after the salt with aluminium, sodium and magnesium (or lithium) is mixed in proportion, and directly does medium with powder ball milling 5～20 hours with dehydrated alcohol, oven dry, and sieving obtains precursor powder.
Beneficial effect:
The present invention adopts microwave method sintering Na-β " Al
2O
3The advantages such as solid electrolyte, microwave heating have from inside to outside, selectivity is good, homogeneous heating, temperature rise rate high, and energy consumption is low can shorten sintering time and inhibiting grain growth with microwave heating.Be specially adapted to Na-β " Al
2O
3Solid electrolyte, the Na that avoids long-time high temperature sintering to cause
2O runs off, and this material has good Microwave Absorption Properties, can improve its density, reduces grain boundary resistance, improves ionic conductivity, thereby improves the performance of beta battery.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 product;
Fig. 2 is the XRD figure of the embodiment of the invention 2 products;
Fig. 3 is the SEM figure of the embodiment of the invention 2 products;
Fig. 4 is that the embodiment of the invention 2 product differing tempss are to the trend map of specific conductivity.
Embodiment
The present invention is described in detail below by specific examples, but protection scope of the present invention is not subject to these examples of implementation.
With Al (NO
3)
39H
2O (A.R.), NaNO
3(A.R.) and Mg (NO
3)
2(A.R.) be raw material, macromolecular compound is citric acid (A.R.), and polyoxyethylene glycol is as dispersion agent.Take by weighing aluminum nitrate 25.8g, SODIUMNITRATE 0.95g, magnesium nitrate 0.66g add 45ml distilled water, and 60 ℃ of lower thermostatically heating, stirring form uniform solution.Then to wherein adding the 16.9g citric acid, and the polyoxyethylene glycol of 2.45g, continue heated and stirred, formed gradually wet gel through 8 hours.200 ℃ of oven dry in the wet gel dislocation baking oven that obtains are obtained xerogel.Then gel was calcined 2 hours under 1250 ℃, temperature rise rate is 3 ℃/min, and 600 ℃ of insulations 2 hours, is beneficial to organic abundant decomposition, obtains superfine powder.With dehydrated alcohol as medium with powder ball milling 8 hours, the oven dry, sieve.It is the disk of 20mm that the gained powder is become diameter in static pressure such as 300MPa, in microwave agglomerating furnace, temperature rise rate is 12 ℃/min, at 1450 ℃ of insulation 15min, continuation is warming up to 1525 ℃ of insulation 15min with the speed of 15 ℃/min, thereupon cooling, and in temperature-fall period, quench, 1450 ℃ of insulation 60min obtain Na-β " Al
2O
3Ceramic electrolyte.Fig. 1 is the XRD figure of gained sample." phase content reaches 96%. to the β of gained sample
Embodiment 2
With Al (NO
3)
39H
2O (A.R.), NaNO
3(A.R.) and Mg (NO
3)
2(A.R.) be raw material, macromolecular compound is citric acid (A.R.), and polyvinyl alcohol is as dispersion agent.Take by weighing aluminum nitrate 38.74g, SODIUMNITRATE 1.42g, magnesium nitrate 0.99g add 50ml distilled water, and 80 ℃ of lower thermostatically heating, stirring form uniform solution.Then to wherein adding the 25.36g citric acid, and the polyvinyl alcohol of 2.79g, continue heated and stirred, formed gradually wet gel through 6 hours.250 ℃ of oven dry in the wet gel dislocation baking oven that obtains are obtained xerogel.Then gel was calcined 3 hours under 850 ℃, temperature rise rate is 2 ℃/min, and 500 ℃ of insulations 2 hours, is beneficial to organic abundant decomposition, obtains superfine powder.With dehydrated alcohol as medium with powder ball milling 5 hours, the oven dry, sieve.It is the disk of 20mm that the gained powder is become diameter in static pressure such as 300MPa, in microwave agglomerating furnace, temperature rise rate is 15 ℃/min, at 1450 ℃ of insulation 30min, continue to be warming up to 1550 ℃ of insulation 3min, thereupon coolings with the speed of 10 ℃/min, and in temperature-fall period, quench, 1500 ℃ of insulation 15min, 1450 ℃ of insulation 30min obtain Na-β " Al
2O
3Ceramic electrolyte.Fig. 2 is the XRD figure of gained sample.As seen from Figure 2, with respect to example 1, the position of each diffraction peak of XRD figure of synthetic product and relative intensity more meet Na-β " Al
2O
3Standard card, " phase content reaches 98% to β.Fig. 3 is the profile scanning photo of gained sample, has formed fine and close sintered compact, and relative density is 98.8%.Fig. 4 be the sample differing temps to the trend map of specific conductivity, along with the rising of temperature, the sample specific conductivity improves.
Embodiment 3
Take by weighing Al
2O
38.94g, Na
2CO
31.78g, Li
2CO
30.056g, put into the agate tank, take raw spirit as medium, mixing and ball milling 15 hours is crossed 200 mesh sieves, 80 ℃ of oven dry in baking oven, it is the disk of 20mm that the gained powder is become diameter in static pressure such as 300MPa, put into microwave agglomerating furnace, with the speed intensification of 10 ℃/min, and at 1425 ℃ of insulation 60min, then be warming up to the cooling of quenching behind 1550 ℃ of insulation 30min with the speed of 12 ℃/min, at 1475 ℃ of insulation 30min, 1450 ℃ of insulation 15min obtain β " Al
2O
3Ceramic electrolyte.
Embodiment 4
With Al (NO
3)
39H
2O (A.R.), NaNO
3(A.R.) and LiNO
3(A.R.) be raw material, urea (A.R.) is as the combustion agent.Take by weighing aluminum nitrate 40g, SODIUMNITRATE 1.41g, lithium nitrate 0.23g add 55ml distilled water, and 65 ℃ of lower thermostatically heating, stirring form uniform solution.Then to wherein adding 11.6g urea, continue heated and stirred, evaporated gradually moisture through 8 hours, continue heating and make its burning, obtain powder.The powder that obtains was calcined 2 hours under 1050 ℃, and temperature rise rate is 3 ℃/min, and 500 ℃ of insulations 2 hours, is beneficial to organic abundant decomposition, obtains superfine powder.With dehydrated alcohol as medium with powder ball milling 6 hours, the oven dry, sieve.It is the disk of 20mm that the gained powder is become diameter in static pressure such as 300MPa, in microwave agglomerating furnace, is warming up to 1400 ℃ with the speed of 15 ℃/min, and then the speed with 10 ℃/min is warming up to 1500 ℃, naturally lowers the temperature behind the insulation 60min, obtains β " Al
2O
3Ceramic electrolyte.
Claims (4)
1. Na-β " Al
2O
3Method for preparing solid electrolyte, concrete steps are: (1) gets the salt that contains aluminium, sodium and magnesium, be dissolved in the solvent, be Na according to target product
1+xO Al
11-xMg
xO
16In the stoichiometric ratio weighing of metallic element be mixed to get mixing solutions, 0.45＜x＜1.0 wherein; Perhaps getting the salt that contains aluminium, sodium and lithium, be dissolved in the solvent, is Na according to target product
1+2yOAl
11-yLi
yO
16In the stoichiometric ratio weighing of metallic element be mixed to get mixing solutions, 0.2＜y＜0.5 wherein; (2) add a kind of and dispersion agent in citric acid, oxalic acid or the tartrate in above-mentioned mixing solutions, heating, stir, reaction obtains wet gel; Wherein the mol ratio of a kind of add-on in citric acid, oxalic acid or the tartrate and all metallic cation sums is 0.5 ~ 2:1; The add-on of dispersion agent and the mol ratio of macromolecular compound are 0.5 ~ 2:2; (3) with the wet gel oven dry that obtains, obtain xerogel; (4) with the xerogel calcining, obtain precursor powder; Wherein controlling temperature rise rate is 100 ~ 200 ℃/hour, and being warming up to sintering temperature is 800 ~ 1400 ℃, and soaking time is 1 ~ 5 hour; (5) with after the presoma granulation that obtains, the moulding, put into microwave oven, wherein the output rating of microwave oven is 3kW ~ 6kW, adopt the mode of Fractional Heat-treatment, the speed of namely controlling 10 ~ 15 ℃/min is warming up to 1350 ~ 1450 ℃, is incubated after 10 ~ 60 minutes, continuation is warming up to 1500-1550 ℃ with the speed of 10 ~ 15 ℃/min, be incubated 3 ~ 60 minutes, and then 1400 ~ 1500 ℃ of quenchings, be incubated 15-60 minute and obtain Na-β " Al
2O
3Solid electrolyte.
2. method according to claim 1 is characterized in that described salt is nitrate, carbonate, chlorate, acetate, Citrate trianion, oxalate, formate or lactic acid salt.
3. method according to claim 1 is characterized in that described dispersion agent is polyvinyl alcohol or polyoxyethylene glycol.
4. method according to claim 1 is characterized in that the thermostatically heating temperature is 60-100 ℃ in the step (2), reacts 6 ~ 30 hours; Bake out temperature is 200 ~ 300 ℃ in the step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102644290A CN101734911B (en) | 2009-12-22 | 2009-12-22 | Preparation method of Na-beta''-Al2O3 solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102644290A CN101734911B (en) | 2009-12-22 | 2009-12-22 | Preparation method of Na-beta''-Al2O3 solid electrolyte |
Publications (2)
| Publication Number | Publication Date |
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| CN101734911A CN101734911A (en) | 2010-06-16 |
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| US9257698B2 (en) * | 2007-01-25 | 2016-02-09 | General Electric Company | Composition, energy storage device, and related process |
| CN101941835B (en) * | 2010-09-15 | 2013-01-16 | 张冰青 | Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same |
| CN102367210A (en) * | 2010-10-29 | 2012-03-07 | 大连路明发光科技股份有限公司 | Preparation method of Na-beta-Al2O3 powder |
| CN104103859A (en) * | 2013-04-15 | 2014-10-15 | 成都慧成科技有限责任公司 | Preparation method for solid electrolyte beta''-Al2O3 powder |
| CN104282868B (en) * | 2013-07-12 | 2016-08-10 | 中国科学院上海硅酸盐研究所 | Electrolyte ceramics barrier film that modified perforated membrane supports and preparation method thereof |
| CN103964822B (en) * | 2014-04-02 | 2016-01-27 | 芜湖浙鑫新能源有限公司 | A kind of sol-gal process that adopts prepares sintering Na-β "-Al 2o 3the method of solid electrolyte precursor |
| CN104143661B (en) * | 2014-07-31 | 2016-08-24 | 南京工业大学 | A kind of high intensity beta-Al2o3method for preparing solid electrolyte |
| CN108408708A (en) * | 2018-03-14 | 2018-08-17 | 华侨大学 | The preparation method of crystalline state LAGP solid electrolyte sheets |
| CN111422892A (en) * | 2020-04-02 | 2020-07-17 | 西南科技大学 | Cubic gamma-AlOOH precursor, Na- β' -Al2O3 solid electrolyte powder and preparation method thereof |
| CN113654936B (en) * | 2021-06-28 | 2024-01-23 | 浙江安力能源有限公司 | Na-beta' -Al 2 O 3 Method for measuring sodium content in solid electrolyte |
| CN114614082B (en) * | 2022-03-24 | 2024-03-12 | 西北核技术研究所 | Preparation method of sodium beta alumina solid electrolyte with high ion conductivity |
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| CN86100599A (en) * | 1986-06-18 | 1987-12-30 | 中国科学院上海硅酸盐研究所 | Solid electrolyte that protecting cathode of overhead metal pipe is used and preparation method thereof |
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| CN86100599A (en) * | 1986-06-18 | 1987-12-30 | 中国科学院上海硅酸盐研究所 | Solid electrolyte that protecting cathode of overhead metal pipe is used and preparation method thereof |
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| Tom Mathews.Solution combustion synthesis of magnesium compensated sodium-β-aluminas.《Materials Science and Engineering B》.2000,第78卷第39-43页. * |
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