CN101941835B

CN101941835B - Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same

Info

Publication number: CN101941835B
Application number: CN2010102860610A
Authority: CN
Inventors: 张冰青; 张祎晶
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-09-15
Filing date: 2010-09-15
Publication date: 2013-01-16
Anticipated expiration: 2030-09-15
Also published as: CN101941835A

Abstract

The invention relates to a preparation method of a Ba ion doped Na-beta'-Al2O3 solid electrolyte and a solid electrolyte prepared by using the same. In the method, a salt containing metal sodium and aluminum is used as a raw material, a salt containing metal lithium or magnesium is used as a stabilizing agent, a salt containing metal barium is especially used as a regulating agent, three precursor powders comprising Na2O.5Al2O3, Li2O.5Al2O3 or MgO.5Al2O3, and BaO.5AL2O3 are respectively prepared by using a sol-gel method, and the target product of (1-3x)Na2O.2xMgO.xBaO.5Al2O3 or (1-3x)Na2O.2xLiO.xBaO.5Al2O3 is prepared, wherein x is greater than 0.02 and smaller than 0.1. Compared with a Na-beta'-Al2O3 solid electrolyte prepared by the conventional method, the Na-beta'-Al2O3 solid electrolyte prepared by the method has the characteristics of higher density, higher strength and higher conductivity, the degradation problem of the solid electrolyte is solved, the service life is prolonged, and thus, the solid electrolyte has wide application prospect.

Description

Na-β " the A1 of doping Ba ion 2O 3Method for preparing solid electrolyte and solid electrolyte prepared by this method

Technical field

The present invention relates to a kind of method for preparing solid electrolyte and solid electrolyte prepared by this method, particularly a kind of Na-β " Al ₂O ₃Method for preparing solid electrolyte and solid electrolyte prepared by this method.

Background technology

The solid electrolyte fast-ionic conductor that is otherwise known as is characterized in depending on ion (or room) and moves to realize conduction from a crystallographic site to a contiguous crystallographic site, and its specific conductivity can reach σ 〉=10 ^-2Ω ^-1Cm ^-1Wherein, Na-β " Al ₂O ₃(desirable chemical formula Na ₂O5.33Al ₂O ₃, be a kind of of many sodium aluminates) and be a kind of cation solid-electrolyte, mainly conduct electricity by the migration of sodium ion.

About Na-β " Al ₂O ₃The electrical conduction mechanism of solid electrolyte, known in the state of the art in its layered crystal structure, three layers of spinel layer that is made of oxonium ion and aluminum ion are arranged in each structure cell.Spinel is a kind of mineral name that contains aluminium, oxygen, because these layers have spinel mineral one spline structure in many sodium aluminates, so often again these layers are called the spinel matrix.Between levels spinel matrix, be by Na ⁺And O ^2-The sodium oxygen layer of the fluff packing that ion consists of contains many rooms, and therefore, sodium ion is easy to migration in sodium oxygen layer, sodium oxygen layer thereby have the effect of transmitting electric charge and material migration, the reason of Here it is ionic conduction.Research is found, at Na-β " Al ₂O ₃In the solid electrolyte sodium oxygen layer structure, there are BR (Beevers-Ross sites) and two kinds of positions of MO (mid-oxygen sites) to occupy for conducting ion, sodium ion mainly occupies the BR position and has the room conduction mechanism, when sodium ion occupies all BR positions or excessive concentration, can't move by the room, so specific conductivity is very low; And the sodium ion of proper concn increases the BR vacancy concentration when occupying the BR position, and specific conductivity increases.But because this crystalline network, sodium ion can only move between the layers, and is irremovable in the direction of perpendicular layers, and therefore this conduction has anisotropic characteristics.

Na-β " Al ₂O ₃Solid electrolyte is with a wide range of applications in energy field, such as high energy sodium-sulfur cell, sodium nickelous chloride battery, sodium heat engine etc.Wherein, sodium-sulfur cell is one of its of paramount importance Application Areas.Sodium-sulfur cell be U.S.'s Ford (Ford) company in 1967 Invention Announce at first, the so far history about 40 years.Na-β " Al wherein ₂O ₃Solid electrolyte consists of the barrier film of sodium-sulfur cell, is the core material of sodium-sulfur cell.Sodium-sulfur cell has the following advantages: energy density is large, its theoretical specific energy (being the available point energy that battery unit mass or unit volume have) is up to 760wh/kg, practical application can reach 390kw/kg, four times of lithium cell, five times of nickel-based battery, ten times of lead-acid cell can be rated as in the world state-of-the-art energy-storage battery; Can realize heavy-current discharge, current density can reach 200-300mA/cm ², and instantaneous time can be emitted the energy of its 3C; Duration of charging is short, and a duration of charging is about 20 to 30 minutes; Long service life discharges and recharges nearly 20,000 times continuously, and work-ing life can be for 15 years; Without self-discharge phenomenon, adopt solid electrolyte, so usually do not adopt the sort of self-discharge and the side reaction of liquid electrolytic electrolitc secondary cell; Efficiency for charge-discharge is high, and enclosed pasture efficient is up to 100%; Volume is little, lightweight, automobile with one about one cubic metre, nearly weigh 300 kilograms high-power sodium-sulfur cell, i.e. once charge more than 800 kilometer of wheeled of motor bus, car once charges and can exercise more than 1200 kilometer; Pollution-free, recyclable, manufacturing processed can not meet national new forms of energy standard fully to environment, and simple substance Na and S element be to the human body nontoxicity, and the Na in the waste and old high-power sodium-sulfur cell and the S rate of recovery are near 100%; The elementary cell of sodium-sulfur cell is cell, and the cell maximum capacity that is used for energy storage reaches 650 ampere-hours, more than the power 120W; To form module after a plurality of cell combinations, the power of module is generally tens of kilowatts, can be directly used in energy storage; Safe and reliable, firm in structure, durable.

Sodium-sulfur cell is in the field such as stable output, distributed power supply, emergency source of electric power, military satellite and the submarine power supply of power station energy storage, electromobile, renewable energy source (wind-force, morning and evening tides and solar electrical energy generation etc.) generating and improve the aspect such as power quality and be widely used, being a kind of battery that manufacturing cost is minimum, the energy return rate is the highest, technology maturity is high in the existing various secondary energy storage battery, also is at present unique commercial energy-storage battery that enters; Relate to a plurality of industries such as industry, commerce, traffic, electric power, the potential a kind of advanced energy-storage battery of tool has a wide range of applications and economic benefit.The sodium-sulfur cell electromobile has successively been assembled by the YUASA of the Ford of the U.S., Japan, the BBC of Britain and railway laboratory, the ABB of Germany, the Mink company of the U.S. etc.And carried out long-term road and tried.Wherein Japanese NGK company is in the world sodium sulphur energy-storage battery development, development and the significant mechanism that uses.At present, existing more than 100 sodium-sulfur battery energy storages of NGK stand in global in service.In July, 2004, the NAs energy storage station (9.6Mw/57.6Mwh) of maximum formally put into operation in Japan in the world.The power at maximum sodium-sulfur battery energy storage station reaches 20Mw in the design, is the maximum chemical power source energy storage station in the present whole world.

In addition, with Na-β " Al ₂O ₃Solid electrolyte is the ion selectivity permeable membrane, can make take liquid alkali metal or gaseous bases metal as the direct transmodulator of the thermoelectric energy of cycle fluid, it is the sodium heat engine, conversion efficiency of thermoelectric can reach 30～40% in theory, applicable heat source temperature scope is 800～1200K, and be applicable to nuclear energy, the fossil energy, the thermal source of the various ways such as sun power, it is simple in structure, reliable operation, higher power density is arranged, high effect cleaning, no matter be or distributed power source portable as ground, or the power supply of space probe, good application prospect is arranged, arouse extensive attention at home and abroad.

Na-β " Al ₂O ₃The preparation of solid electrolyte can be divided into four steps usually: the first, Na-β " Al ₂O ₃Producing of solid electrolyte precursor powder; The second, Na-β " Al ₂O ₃The shaping forming of solid electrolyte; The 3rd, Na-β " Al ₂O ₃Burning till of solid electrolyte; The 4th, Na-β " Al ₂O ₃The quenching of solid electrolyte.Known β " Al ₂O ₃Unstable in the high temperature sintering process, can occur to β-Al ₂O ₃Mutually transformation, thereby specific conductivity is significantly reduced.Usually improve β " Al by doped with Mg O or LiO in the prior art ₂O ₃Phase stability at high temperature.Na-β " Al ₂O ₃Method for preparing solid electrolyte is a lot, and partial synthesis method, reaction sintering, spray-drying process, sol-gel method, microwave sintering method, supercritical solvent desiccating method etc. are arranged.

Chen Kun is firm etc., " the standby Na-β " Al of partial synthesis legal system ₂O ₃Pottery ", inorganic salt material journal, adopts high-purity ultra-fine a-Al at the 5th phase of the 12nd volume October in 1997 ₂O ₃Powder, analytically pure sodium oxalate and lithium oxalate (or yellow soda ash and Quilonum Retard) are made raw material, press first Li ₂O: 5Al ₂O ₃And Na ₂O: 5Al ₂O ₃Proportion of composing batching, at 1250 ℃ of insulation 2h, respectively pre-synthesis Li ₂O-5Al ₂O ₃And Na ₂O-5Al ₂O ₃Then powder makes secondary raw material with them, presses Li ₂Na-β " the Al that O is stable ₂O ₃Proportion of composing batching is made the medium ball milling with raw spirit, adds polyvinyl butyral as binding agent, drying, and granulating with the pressure isostatic pressing of 300MPa, is pressed into the 20mm disk and φ 13.5 * 180mm wall thickness is the pipe of 1.8mm.After removing binding agent, use the platinum foil package, hold in both hands in the electric furnace at box silicon molybdenum and burn till.

Zhang Lili etc., " microwave-assisted SolGel method is synthesized Na-β " Al ₂O ₃Electrolyte powder ", the silicate circular, in February, 2007, the 1st phase of the 26th volume, use analytically pure aluminum nitrate, yellow soda ash and magnesium nitrate, the difference wiring solution-forming, chemical formula is (Na _1+yOAl _11-yMg _yO ₁₆), after quantitative analysis, press y=0.67 (Na _1.67OAl _10.33Mg _0.67O ₁₆) stoichiometric ratio be made into mixing solutions.Add a certain amount of citric acid and polyvinyl alcohol, wherein the mole number of citric acid equals all metallic cation mole number sums in the solution, makes gel at 80 ℃ of lower slow evaporation moisture.Then gel is decomposed under the temperature of 1073～1373K and obtain preburning powder.

Chinese patent application publication No. CN101717259A, " a kind of employing sol-gel method prepares Na-β " Al ₂O ₃The method of solid electrolyte precursor "; sodium nitrate aqueous solution, dehydrated alcohol, nine water aluminum nitrates and the citric acid of an amount of weight ratio 4.0-8.0% are configured to faint yellow vitreosol C; then add the ethylene glycol additive in the colloidal sol C and be configured to clear gel D, with gel D behind the dry and ball milling fluffy powder.This powder namely gets Na-β " Al at 850 ℃～950 ℃ insulation 1～4h ₂O ₃The solid electrolyte precursor ultrafine powder.Wherein, the mol ratio of Na and Al element is 1: 5.33, and the volume ratio of deionized water and dehydrated alcohol is 1: 4, and the volume ratio of ethylene glycol and deionized water is (0～2): 1, and the mol ratio of metallic cation and citric acid is 1 in the colloidal sol: (0.5～3).

Chinese patent application publication No. CN101734911A, " a kind of Na-β " Al ₂O ₃Method for preparing solid electrolyte ", 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.

In order to obtain the Na-β " Al of specific energy height, long service life ₂O ₃Solid electrolyte requires that it has that high electricity is led, high-density and high strength, also needs in addition to have very uniformly microstructure and composition profiles.Na-β " Al ₂O ₃These performances of solid electrolyte depend on chemical constitution and preparation technology strongly.Usually, the Na-β " Al that makes of above-mentioned these preparation methods ₂O ₃In use there is serious degradation phenomena in solid electrolyte, causes electrolytic conductivity to reduce or inefficacy.Cause the one of the main reasons of the problems referred to above to be: the migration of sodium ion causes sodian deposition, makes Na-β " Al ₂O ₃Produce tiny crack in the solid electrolyte, and finally cause the destruction of material structure and performance.In addition, people wish further to improve Na-β " Al ₂O ₃The specific conductivity of solid electrolyte is so that the larger effect of its performance.

On the other hand, barium ion known in the state of the art is unique at β " Al ₂O ₃Only occupy the BR position mutually and do not occupy the divalent ion of MO position.The people such as A1EXANDER PECHENIK, the Monte Carlo study of the divalence in Divalentand Mixed Divalent/Monovalent Conduction in β " Alumina:A MonteCarlo Study (β "-aluminum oxide and divalence/monovalence conduction), JOURNA1 OF SOLID STATE CHEMISTRY, 58,103-113 (1985), by the Monte Carlo calculations method, foretell theoretically " the Al at Na-β ₂O ₃In, partly replace sodium ion with barium ion, can increase the BR vacancy concentration, thereby improve Na-β " Al ₂O ₃The solid electrolyte specific conductivity.

But above-mentioned research only limits to the Theoretical Calculation stage.According to the inventor's understanding, the Na-β " Al of couple doping BaO is arranged not yet ₂O ₃The report of method for preparing solid electrolyte and actual performance research thereof also there is not yet in industrial practice the Na-β " Al with doping BaO ₂O ₃Solid electrolyte application is in various conventional fields.

Summary of the invention

The inventor has obtained a kind of Na-β " Al for preparing doping Ba ion after deliberation ₂O ₃The method of solid electrolyte, take the salt of containing metal sodium, aluminium as raw material, the salt of containing metal lithium or magnesium is stablizer, and the salt of containing metal barium is conditioning agent, adds respectively solvent, complexing agent, dispersion agent and pH value conditioning agent, make precursor powder, with precursor powder granulation, hydrostatic profile, make biscuit, burn till, then quench, obtain Na-β " Al ₂O ₃The solid electrolyte finished product.

Na-β " the Al of a kind of Ba ion that mixes that the present invention proposes ₂O ₃Method for preparing solid electrolyte specifically may further comprise the steps:

1, according to the chemical formula Na of intermediate objective product ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃Or MgO5Al ₂O ₃, BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing respectively sodium Metal 99.5 and aluminium salt, take by weighing metallic lithium or magnesium and aluminium salt, take by weighing barium metal and aluminium salt, each group salt is dissolved in respectively in the solvent preparation obtains three kinds of solution;

2, in above-mentioned three kinds of solution, add complexing agent, dispersion agent and pH value conditioning agent respectively and mix, heat, react, obtain three kinds of colloidal sols;

Three kinds of colloidal sols that 3, will obtain carry out drying, obtain three kinds of xerogel;

After three kinds of xerogel pre-burnings that 4, will obtain respectively, the thermal treatment, obtain Na-β " Al ₂O ₃Three kinds of precursor powders, i.e. Na of solid electrolyte ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃Or MgO5Al ₂O ₃, BaO5Al ₂O ₃

5, according to chemical formula (1-3x) Na of target product ₂O2xMgOxBaO5Al ₂O ₃Or (1-3x) Na ₂O2x Li ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein 0.02＜x＜0.1 takes by weighing respectively precursor powder, configuration precursor powder mixture;

6, described precursor powder mixture is added solvent, plastic agent and binding agent, through ball milling, obtain slurry;

7, with the slurry granulation that obtains, hydrostatic profile is made biscuit;

8, the biscuit of making is burnt till, then quench, naturally cool to room temperature, obtain the Na-β " Al of doping Ba ion ₂O ₃The solid electrolyte finished product.

A preferred embodiment of the method according to this invention, in step 1, the salt of described sodium Metal 99.5, aluminium, lithium or magnesium and barium is soluble inorganic salt and/or solubility organic salt; Solvent is deionized water and/or low-carbon alcohol; The volumetric molar concentration of the solution that configuration obtains is 0.2-1mol/L.

A preferred embodiment of the method according to this invention, in step 1, the soluble salt of described aluminium is selected from Al (NO ₃) ₃9H ₂O, aluminum triacetate, aluminium triformate or their mixture; The soluble salt of sodium is selected from SODIUMNITRATE, sodium acetate, sodium oxalate or their mixture; The soluble salt of lithium is selected from lithium nitrate, lithium acetate, lithium oxalate or their mixture; The soluble salt of barium is selected from nitrate of baryta, barium acetate, barium oxalate or their mixture; The soluble salt of magnesium is selected from magnesium nitrate, magnesium acetate, magnesium oxalate or their mixture; Low-carbon alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol or their mixture.

A preferred embodiment of the method according to this invention, in step 2, described complexing agent is the organic acid complexing agent; Dispersion agent is ethoxy compound and/or ethylene oxide based compound; PH value conditioning agent is ammoniacal liquor and/or organic amine compound, and regulator solution pH value scope is between the 1-7; It is 1 that the complexing agent addition makes the ratio of all metallic cation mole numbers in complexing agent and the solution: (1-3); The addition of dispersion agent is the 0.2-3wt% of all metal-salt sums in the solution; The temperature rise rate of reacting by heating process was 10-15 ℃/minute, 50-70 ℃ of insulation 1-2 hour.

A preferred embodiment of the method according to this invention, in step 2, described organic acid complexing agent is selected from EDTA, Thiovanic acid, citric acid, tartrate, oxalic acid, lactic acid or their mixture; Ethoxy compound in the described dispersion agent is alkylphenol polyoxyethylene, and the ethylene oxide based compound is polyoxyethylene (PEO); Organic amine compound in the pH adjusting agent is selected from quadrol, trolamine or their mixture.

A preferred embodiment of the method according to this invention, in step 2, described alkylphenol polyoxyethylene is selected from C5-C10 alkylphenol polyoxyethylene or their mixture, and wherein the number of ethylene oxide unit is 50-100, preferred 50-60; The molecular weight ranges of described polyoxyethylene (PEO) is 400-1000 ten thousand dalton, preferred 400-600 ten thousand dalton.

A preferred embodiment of the method according to this invention, in step 3, the temperature rise rate of described drying process was 5-10 ℃/minute, 80-120 ℃ of insulation 4-6 hour.

A preferred embodiment of the method according to this invention, in step 4, the temperature rise rate of described xerogel pre-burning process is 3-5 ℃/minute, respectively 150-200 ℃, 600-800 ℃ insulation 1-2 hour; The temperature rise rate of heat treatment process was 3-5 ℃/minute, 1000-1250 ℃ of insulation 1-2 hour.

A preferred embodiment of the method according to this invention, in step 6, described solvent is selected from ethanol, propyl alcohol, Virahol, ethylene dichloride, trichloroethane or their mixture; Plastic agent is selected from ethylene glycol, polyoxyethylene glycol, dibutyl phthalate or their mixture; Binding agent is selected from polyvinyl butyral acetal (PVB), polymethyl acrylate, ethyl cellulose or their mixture; The weight ratio of the addition of solvent and described precursor powder mixture is (1.5-4): 1; Content of binder is the 3-10wt% of described precursor powder mixture; The weight ratio of plastic agent and binding agent is (1-5): 1; Ball-milling Time is 4-6h.

A preferred embodiment of the method according to this invention, in step 7, the temperature in the described granulation process is 120-200 ℃; The pressure-controlling of hydrostatic profile process is at 300-350MPa.

A preferred embodiment of the method according to this invention, in step 8, the temperature rise rate of described sintering process is 2-3 ℃/minute, respectively 1400-1500 ℃ of insulation 1-2 hour, 1580-1620 ℃ is incubated 0.2-0.5 hour; The rate of temperature fall of quenching process was 2-3 ℃/minute, 1400-1500 ℃ of insulation 1-2 hour.

Fig. 1 shows the schema of method of the present invention.

In yet another aspect, the present invention provides the Na-β " Al of doping Ba ion by above-mentioned either method ₂O ₃Solid electrolyte.

Advantage of the present invention and the positively effect that reaches are: the Na-β " Al of the doping Ba ion of prepared in accordance with the method for the present invention ₂O ₃Solid electrolyte, particle size distribution range is narrow, homogeneous chemical composition, and with prior art in the do not mix Na-β " Al of Ba ion ₂O ₃Solid electrolyte is compared has higher specific conductivity.In addition, the inventor also is surprised to find that, in preparation process, adds an amount of Ba ion and has alleviated to a certain extent Na-β " Al ₂O ₃The degenerate problem of solid electrolyte.The inventor thinks, because the Ba ion only occupies the BR room, can not fetter adjacent BR room and MO room, the conduction of the sodium ion that the passage that therefore forms by BR and MO position spreads keeps unimpeded, therefore avoid the deposition of sodium, thereby effectively hindered Na-β " Al ₂O ₃The degeneration of solid electrolyte.Na-β " the Al of the doping Ba ion that therefore, makes according to the present invention ₂O ₃Solid electrolyte has high-density and high strength simultaneously, has further improved specific conductivity, and has significantly improved Na-β " Al ₂O ₃The work-ing life of solid electrolyte.

Description of drawings

Fig. 1 is preparation Na-β " Al ₂O ₃The schema of solid electrolyte;

Fig. 2 is embodiment 1Na ₂O5Al ₂O ₃The XRD figure of precursor powder;

Fig. 3 is embodiment 1Li ₂O5Al ₂O ₃The XRD figure of precursor powder;

Fig. 4 is embodiment 1BaO5Al ₂O ₃The XRD figure of precursor powder;

Fig. 5 is embodiment 1Na-β " Al ₂O ₃The XRD figure of solid electrolyte;

Fig. 6 is embodiment 1Na-β " Al ₂O ₃The SEM figure of solid electrolyte.

Embodiment

Comparative example 1

Take by weighing aluminum nitrate (A.R) 38.74g, SODIUMNITRATE (A.R) 1.42g, magnesium nitrate (A.R) 0.99g adds 50ml distilled water, and 80 ℃ of lower thermostatically heating, stirring form uniform solution.Then to wherein adding 25.36g citric acid (A.R) and 2.79g polyvinyl alcohol, continue heated and stirred, formed gradually wet gel through 6 hours.The wet gel that obtains moved to 250 ℃ of oven dry obtain xerogel in the baking oven.Then gel was calcined 3 hours under 850 ℃, heat-up rate is 2 ℃/min, 500 ℃ of insulations 2 hours, obtains powder.With dehydrated alcohol as medium with powder ball milling 5 hours, oven dry is sieved.The gained powder is become the disk of diameter 20mm in static pressure such as 300MPa, in microwave agglomerating furnace, 15 ℃/min of heat-up rate at 1450 ℃ of insulation 30min, continues to be warming up to 1550 ℃ of insulation 3min with the speed of 10 ℃/min, thereupon cooling, and in temperature-fall period, quench 1500 ℃ of insulation 15min, 1450 ℃ of insulation 30min, naturally cool to room temperature, obtain comparative sample 1 '.

Comparative example 2

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Being stablizer, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃And Li ₂O5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2832 the gram NaNO ₃Reach 403.4762 gram Al (NO ₃) ₃9H ₂O takes by weighing 3.4326 gram LiNO ₃Reach 93.3839 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes respectively two kinds of solution of 0.5mol/L.In above-mentioned two kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O 135.5857 grams, 31.3868 grams, be the 1wt% of all metal-salt sums in the various solution by dispersion agent, add respectively polyoxyethylene (PEO-600) 2.4737 grams, 0.5645 gram, regulate pH=3 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains respectively two kinds of colloidal sols, with two kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain respectively xerogel.Carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Two kinds of precursor powders of solid electrolyte.

Be (1-2x) Na according to the target product chemical formula ₂O2xLi ₂O5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 60.3412 gram and Li ₂O5Al ₂O ₃Precursor powder 8.1363 grams, make mixture, weight ratio by solvent and mixture is 2: 1, adding etoh solvent 136.9550 grams, is the 5wt% of mixture by content of binder, adds binding agent polyvinyl butyral acetal (PVB) 3.4239 grams, weight ratio by plastic agent and binding agent is 3: 1, add plastic agent dibutyl phthalate 10.2716 grams, through ball milling 5h, obtain slurry; With granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit with the slurry that obtains; The biscuit of making is burnt till, and sintering process, temperature rise rate are 3 ℃/minute, respectively 1475 ℃ of insulations 2 hours, then 1615 insulations 0.5 hour quench, and quenching process, rate of temperature fall are 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cool to room temperature, obtain comparative sample 2 '.

Embodiment 1

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Be stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 17.1601 the gram NaNO ₃Reach 378.6915 gram Al (NO ₃) ₃9H ₂O; Take by weighing 2.1574 gram LiNO ₃Reach 58.6921 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.0887 gram Ba (NO ₃) ₂Reach 58.6911 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes respectively three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O127.2801 gram, 19.7267 grams, 18.0825 grams, press the 1wt% of all metal-salt sums in dispersion agent and the various solution, add respectively polyoxyethylene (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram, regulate pH=3 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain respectively three kinds of colloidal sols, with three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain respectively xerogel.Carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xLi ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 46.4576 grams, Li ₂O5Al ₂O ₃Precursor powder 6.7461 gram and BaO5Al ₂O ₃Precursor powder 4.1446 grams, make mixture, weight ratio by solvent and mixture is 2: 1, adding etoh solvent 114.6966 grams, is the 5wt% of mixture by content of binder, adds binding agent polyvinyl butyral acetal (PVB) 2.8674 grams, weight ratio by plastic agent and binding agent is 3: 1, add plastic agent dibutyl phthalate 8.6022 grams, through ball milling 5h, obtain slurry; With granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit with the slurry that obtains; The biscuit of making is burnt till, and sintering process, temperature rise rate are 3 ℃/minute, respectively 1475 ℃ of insulations 2 hours, then 1615 insulations 0.5 hour quench, and quenching process, rate of temperature fall are 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cool to room temperature, obtain Na-β " Al ₂O ₃Solid electrolytic quality sample 1.

Embodiment 2

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Be stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 17.1601 the gram NaNO ₃Reach 378.6915 gram Al (NO ₃) ₃9H ₂O; Take by weighing 2.1574 gram LiNO ₃Reach 58.6921 gram Al (NO ₃) ₃9H ₂O takes by weighing 4.0887 gram Ba (NO ₃) ₂Reach 58.6911 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes respectively three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 3 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O84.8534 gram, 13.1511 grams, 12.0550 grams; Press the 0.2wt% of all metal-salt sums in dispersion agent and the various solution, add respectively polyoxyethylene (PEO-600) 0.4644 gram, 0.0710 gram, 0.0748 gram, regulate pH=7 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xLi ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 46.4576 grams, Li ₂O5Al ₂O ₃Precursor powder 6.7461 gram and BaO5Al ₂O ₃Precursor powder 4.1446 grams are made mixture.Weight ratio by solvent and mixture is 2: 1, adds etoh solvent 114.6966 grams; Be the 5wt% of mixture by content of binder, add binding agent polyvinyl butyral acetal (PVB) 2.8674 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 8.6022 grams; Through ball milling 5h, obtain slurry, with granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit with the slurry that obtains.The biscuit of making is burnt till, and sintering process, temperature rise rate are 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The quenching process rate of temperature fall is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 2.

Embodiment 3

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Be stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 17.1601 the gram NaNO ₃Reach 378.6915 gram Al (NO ₃) ₃9H ₂O; Take by weighing 2.1574 gram LiNO ₃Reach 58.6921 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.0887 gram Ba (NO ₃) ₂Reach 58.6911 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 3mol/L.In above-mentioned three kinds of solution, press the ratio 1: 1 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O254.5602 gram, 39.4534 grams, 36.1650 grams, press the 3wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 6.9653 grams, 1.0644 grams, 1.1224 grams, regulate pH=1 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, take temperature rise rate as 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xLi ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 46.4576 grams, Li ₂O5Al ₂O ₃Precursor powder 6.7461 gram and BaO5Al ₂O ₃Precursor powder 4.1446 grams, make mixture, weight ratio by solvent and mixture is 2: 1, adding etoh solvent 114.6966 grams, is the 5wt% of mixture by content of binder, adds binding agent polyvinyl butyral acetal (PVB) 2.8674 grams, weight ratio by plastic agent and binding agent is 3: 1, add plastic agent dibutyl phthalate 8.6022 grams, through ball milling 5h, obtain slurry.With the slurry granulation under 150 ℃ temperature that obtains, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, then 1615 insulations 0.5 hour quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 3.

Embodiment 4

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Be stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 17.1601 the gram NaNO ₃Reach 378.6915 gram Al (NO ₃) ₃9H ₂O; Take by weighing 2.1574 gram LiNO ₃Reach 58.6921 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.0887 gram Ba (NO ₃) ₂Reach 58.6911 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned each solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O127.2801 gram, 19.7267 grams, 18.0825 grams; Press the 1wt% of all metal-salt sums in dispersion agent and the various solution, add respectively polyoxyethylene (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram; Regulate pH=3 with quadrol respectively; And mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xLi ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.02 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 53.7478 grams, Li ₂O5Al ₂O ₃Precursor powder 2.1588 gram and BaO5Al ₂O ₃Precursor powder 1.3263 gram is made mixture, is 2: 1 by the weight ratio of solvent and mixture, add etoh solvent 114.4658 grams, being the 5wt% of mixture by content of binder, adding binding agent polyvinyl butyral acetal (PVB) 2.8616 grams, is 3: 1 by the weight ratio of plastic agent and binding agent, add plastic agent dibutyl phthalate 8.5848 grams, through ball milling 5h, obtain slurry, with the slurry that obtains with granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, then 1615 insulations 0.5 hour quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 3.

Embodiment 5

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, LiNO ₃Be stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 17.1601 the gram NaNO ₃Reach 378.6915 gram Al (NO ₃) ₃9H ₂O; Take by weighing 2.1574 gram LiNO ₃Reach 58.6921 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.0887 gram Ba (NO ₃) ₂Reach 58.6911 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O127.2801 gram, 19.7267 grams, 18.0825 grams; Press the 1wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram; Regulate pH=3 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xLi ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=O.08 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 43.4557 grams, Li ₂O5Al ₂O ₃Precursor powder 8.6350 gram and BaO5Al ₂O ₃Precursor powder 5.3051 grams, make mixture, weight ratio by solvent and mixture is 2: 1, adding etoh solvent 114.7916 grams, is the 5wt% of mixture by content of binder, adds binding agent polyvinyl butyral acetal (PVB) 2.8698 grams, weight ratio by plastic agent and binding agent is 3: 1, add plastic agent dibutyl phthalate 8.6094 grams, through ball milling 5h, obtain slurry.With granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit with the slurry that obtains.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 5.

Embodiment 6

Replace dibutyl phthalates as plastic agent and keep plastic agent and the weight ratio of binding agent is 3: 1 except add 8.6022 gram polyoxyethylene glycol in the mixture of three kinds of precursor powders, remaining embodiment is with embodiment 1.Obtain thus Na-β " Al ₂O ₃Solid electrolytic quality sample 6.

Embodiment 7

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, Mg (NO ₃) ₂6H ₂O is stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, MgO5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2429 the gram NaNO ₃Reach 402.5869 gram Al (NO ₃) ₃9H ₂O; Take by weighing 10.8531 gram Mg (NO ₃) ₂6H ₂O and 158.7856 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.6711 gram Ba (NO ₃) ₂Reach 67.0511 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O 135.3115 grams, 48.9212 grams, 20.6582 grams; Press the 1wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram; Regulate pH=3 with quadrol respectively; And mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xMgOxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 51.6195 grams, MgO5Al ₂O ₃Precursor powder 7.6404 gram and BaO5Al ₂O ₃Precursor powder 4.6051 grams are made mixture.Weight ratio by solvent and mixture is 2: 1; Adding etoh solvent 127.7300 grams, is the 5wt% of mixture by content of binder, adds binding agent polyvinyl butyral acetal (PVB) 3.1933 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 9.5799 grams; Through ball milling 5h, obtain slurry.With granulation under 150 ℃ the temperature, hydrostatic profile under 300MPa is made biscuit with the slurry that obtains.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 7.

Embodiment 8

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, Mg (NO ₃) ₂6H ₂O is stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, MgO5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2429 the gram NaNO ₃Reach 402.5869 gram Al (NO ₃) ₃9H ₂O; Take by weighing 10.8531 gram Mg (NO ₃) ₂6H ₂O and 158.7856 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.6711 gram Ba (NO ₃) ₂Reach 67.0511 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 3 of all metallic cation mole numbers in complexing agent and the three kinds of solution, add respectively C ₆H ₈O ₇H ₂O 90.2077 grams, 32.6142 grams, 13.7722 grams; Press the 0.2wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 0.4937 gram, 0.1929 gram, 0.0855 gram, regulate pH=7 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain three kinds of colloidal sols.With three kinds of colloidal sols that obtain, temperature rise rate is 5 ℃/minute, carries out drying in 4 hours 100 ℃ of insulations, obtains three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xMgOxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 51.6195 grams, MgO5Al ₂O ₃Precursor powder 7.6404 gram and BaO5Al ₂O ₃Precursor powder 4.6051 grams are made mixture.Weight ratio by solvent and mixture is 2: 1, adds etoh solvent 127.7300 grams; Be the 5wt% of mixture by content of binder, add binding agent polyvinyl butyral acetal (PVB) 3.1933 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 9.5799 grams; Through ball milling 5h, obtain slurry.With the slurry granulation under 150 ℃ temperature that obtains, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 8.

Embodiment 9

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, Mg (NO ₃) ₂6H ₂O is stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂0 ₃, MgO5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2429 the gram NaNO ₃Reach 402.5869 gram Al (NO ₃) ₃9H ₂O; Take by weighing 10.8531 gram Mg (NO ₃) ₂6H ₂O and 158.7856 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.6711 gram Ba (NO ₃) ₂Reach 67.0511 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 1 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O 270.6230 grams, 97.8425 grams, 41.3164 grams; Press the 3wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 7.4048 grams, 2.8930 grams, 1.2823 grams, regulate pH=1 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xMgOxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.0625 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 51.6195 grams, MgO5Al ₂O ₃Precursor powder 7.6404 gram and BaO5Al ₂O ₃Precursor powder 4.6051 grams are made mixture.Weight ratio by solvent and mixture is 2: 1, adds etoh solvent 127.7300 grams; Be the 5wt% of mixture by content of binder, add binding agent polyvinyl butyral acetal (PVB) 3.1933 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 9.5799 grams; Through ball milling 5h, obtain slurry.With the slurry granulation under 150 ℃ temperature that obtains, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 9.

Embodiment 10

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, Mg (NO ₃) ₂6H ₂O is stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, MgO5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2429 the gram NaNO ₃Reach 402.5869 gram Al (NO ₃) ₃9H ₂O; Take by weighing 10.8531 gram Mg (NO ₃) ₂6H ₂O and 158.7856 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.6711 gram Ba (NO ₃) ₂Reach 67.0511 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O 135.3115 grams, 48.9212 grams, 20.6582 grams, press the 1wt% of all metal-salt sums in dispersion agent and the three kinds of solution, add respectively polyoxyethylene (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram, regulate pH=3 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, take temperature rise rate as 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xMgOxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.1 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 40.0250 grams, MgO5Al ₂O ₃Precursor powder 11.0022 gram and BaO5Al ₂O ₃Precursor powder 6.6313 grams are made mixture.Weight ratio by solvent and mixture is 2: 1, adds etoh solvent 115.317 grams; Be the 5wt% of mixture by content of binder, add binding agent polyvinyl butyral acetal (PVB) 2.8829 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 8.6487 grams; Through ball milling 5h, obtain slurry.With the slurry granulation under 150 ℃ temperature that obtains, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 10.

Embodiment 11

With NaNO ₃, Al (NO ₃) ₃9H ₂O is raw material, Mg (NO ₃) ₂6H ₂O is stablizer, Ba (NO ₃) ₂Being conditioning agent, is Na according to intermediate objective product chemical formula ₂O5Al ₂O ₃, MgO5Al ₂O ₃And BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing 18.2429 the gram NaNO ₃Reach 402.5869 gram Al (NO ₃) ₃9H ₂O; Take by weighing 10.8531 gram Mg (NO ₃) ₂6H ₂O and 158.7856 gram Al (NO ₃) ₃9H ₂O; Take by weighing 4.6711 gram Ba (NO ₃) ₂Reach 67.0511 gram Al (NO ₃) ₃9H ₂O is dissolved in each group salt respectively in the solvent deionized water, makes three kinds of solution of 0.5mol/L.In above-mentioned three kinds of solution, press the ratio 1: 2 of all metallic cation mole numbers in complexing agent and each solution, add respectively C ₆H ₈O ₇H ₂O 135.3115 grams, 48.9212 grams, 20.6582 grams, press the 1wt% of all metal-salt sums in dispersion agent and each solution, add respectively polyoxyethylene (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram, regulate pH=3 with quadrol respectively, and mix, temperature rise rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, take temperature rise rate as 5 ℃/minute, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Then carry out the pre-burning process, take temperature rise rate as 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, temperature rise rate is 3 ℃/minute, 1250 ℃ of insulations 2 hours, obtains Na-β " Al ₂O ₃Three kinds of precursor powders of solid electrolyte.

Be (1-3x) Na according to the target product chemical formula ₂O2xMgOxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein x=0.02 takes by weighing respectively Na ₂O5Al ₂O ₃Precursor powder 53.7478 grams, MgO5Al ₂O ₃Precursor powder 2.2004 gram and BaO5Al ₂O ₃Precursor powder 1.3263 grams are made mixture.Weight ratio by solvent and mixture is 2: 1, adds etoh solvent 114.5490 grams; Be the 5wt% of mixture by content of binder, add binding agent polyvinyl butyral acetal (PVB) 2.8637 grams; Weight ratio by plastic agent and binding agent is 3: 1, adds plastic agent dibutyl phthalate 8.5911 grams through ball milling 5h, obtains slurry.With the slurry granulation under 150 ℃ temperature that obtains, hydrostatic profile under 300MPa is made biscuit.The biscuit of making is burnt till, and the temperature rise rate of sintering process is 3 ℃/minute, and respectively 1475 ℃ of insulations 2 hours, 1615 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process is 3 ℃/minute, 1475 ℃ of insulations 2 hours, naturally cools to room temperature, obtains Na-β " Al ₂O ₃Solid electrolytic quality sample 11.

Embodiment 12

Embodiment is basic identical with embodiment 7, and difference is, adds 9.5799 gram polyoxyethylene glycol replacement dibutyl phthalates in the mixture of three kinds of precursor powders as plastic agent and keeps plastic agent and the weight ratio of binding agent is 3: 1; The temperature rise rate of sintering process is 2 ℃/minute, and respectively 1455 ℃ of insulations 2 hours, 1595 ℃ are incubated 0.5 hour, then quench.The rate of temperature fall of quenching process was 2 ℃/minute, 1455 ℃ of insulations 2 hours.Obtain thus Na-β " Al ₂O ₃Solid electrolytic quality sample 12.

Comparative example 1 is preparation Na-β " AI ₂O ₃One of ordinary method of solid electrolyte, the specific conductivity of the sample 1 ' that obtains and tiny crack bombardment time have represented the level of prior art.Method method with embodiment 1 except not using BaO that comparative example 2 uses is identical.

For the sample 1 ' that obtains in the above-mentioned comparative example and 2 ' and embodiment in the sample 1-12 that obtains carry out the mensuration of every character, wherein:

Carry out analytical calculation by the x ray diffraction spectra to sample, obtain Na-β " Al ₂O ₃The relative mass content (%) of solid electrolyte phase;

Obtain sample quality by weighing, obtain the volume of sample with drainage, obtain the actual density of sample according to the definition of density, based on theoretical density 3.26g/cm ³Calculate the per-cent of actual density, with this as relative density;

Na-β " Al ₂O ₃The resistivity of solid electrolyte adopts platinum to make electrode with under 300 ℃ of temperature (working temperature of sodium-sulfur cell is generally 275 ℃-350 ℃) condition, measures with the V-A method, gets specific conductivity by formula σ=1/ ρ;

Folding strength is measured and is adopted conventional known three point method (YS/T 63.14-2006) to measure;

Na-β " Al ₂O ₃Solid electrolyte is made the electronic probe sample of δ 1.8 * 3 * 4mm, test at EPMA8705QH, test conditions is as follows: carried out the electronic probe experiment under electric current 50nA, acceleration voltage 20kV, the beam spot diameter 1 μ m, measured the bombardment time that tiny crack appears in each sample, to characterize the degraded performance of solid electrolyte.

Above-mentioned test result is listed in the table 1.

Table 1

By as seen from Table 1 upper: compare with comparative example 1, the sample that embodiments of the invention obtain generally has higher specific conductivity, and has obviously postponed the bombardment time that tiny crack occurs, and its relative density and folding strength also improve to some extent; Compare with comparative example 2, the specific conductivity of the sample that embodiment obtains is higher, has still obviously postponed the bombardment time that tiny crack occurs, and its relative density and folding strength also improve to some extent equally.

In the above-described embodiments, embodiment 1 is preferred embodiment, by the prepared Na-β " Al of embodiment 1 ₂O ₃Solid electrolyte precursor ultrafine powder particle is comparatively even, the Na-β " Al of acquisition ₂O ₃Solid electrolytic quality sample 1 has that high electricity is led, high-density and high-intensity premium properties.

The Na that embodiment 1 is prepared ₂O5AL ₂O ₃The XRD figure of precursor powder as shown in Figure 2, by the prepared Li of embodiment 1 ₂O5AL ₂O ₃The XRD figure of precursor powder as shown in Figure 3, by the prepared BaO5AL of embodiment 1 ₂O ₃The XRD figure of precursor powder precursor powder as shown in Figure 4, the Na-β " Al that is obtained by embodiment 1 ₂O ₃The XRD figure of solid electrolytic quality sample 1 as shown in Figure 5.By above-mentioned collection of illustrative plates as seen, although in three kinds of precursor powders except β " Al ₂O ₃Mutually, also there is other phase of a great deal of, but is the β " Al of homogeneous relatively through the finished product that burns till the solid electrolyte that step obtains ₂O ₃Phase.Na-β " the Al that is obtained by embodiment 1 ₂O ₃The SEM of solid electrolyte schemes as shown in Figure 6, and visible grain-size is about 1-3 μ m, and structure is comparatively fine and close, has therefore obtained higher relative density and folding strength.

Aspect electrical property, the specific conductivity of the sample 1 that embodiment 1 obtains is 1.53 times of sample 1 ' specific conductivity, 1.27 times of sample 2 ' specific conductivity; Occurring aspect the bombardment time of tiny crack, sample 1 is far superior to sample 1 ' and 2 ' especially.

This shows that by adopting method of the present invention, the especially doping of Ba ion has improved Na-β " AI ₂O ₃The specific conductivity of solid electrolyte, its degenerate problem have also obtained the improvement of quite large degree.Therefore, the product that adopts method of the present invention to obtain has broad application prospects.

Can be found out that by above-mentioned all embodiment in concrete implementation process, those skilled in the art can both carry out concrete enforcement according to the specialized range of each processing parameter, is not limited with the given above-described embodiment of the present invention.

By above-mentioned specific embodiment the present invention is described in detail, those skilled in the art can understand, in the scope that does not exceed spirit of the present invention and essence, certain modification and distortion to the present invention makes still can realize result of the present invention.

Claims

1. the Na-β " Al of the Ba ion that mixes ₂O ₃Method for preparing solid electrolyte is characterized in that, described method is take the salt of containing metal sodium, aluminium as raw material, and the salt of containing metal lithium or magnesium is stablizer, and the salt of containing metal barium is conditioning agent, comprises the steps:

(1), according to the chemical formula Na of target precursor powder ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃Or MgO5Al ₂O ₃, BaO5Al ₂O ₃The metallic element stoichiometric ratio, take by weighing respectively sodium Metal 99.5 and aluminium salt, take by weighing metallic lithium or magnesium and aluminium salt, take by weighing barium metal and aluminium salt, each group salt is dissolved in respectively in the solvent preparation obtains three kinds of solution;

(2), in above-mentioned three kinds of solution, add complexing agent, dispersion agent and pH value conditioning agent respectively and mix, heat, react, obtain three kinds of colloidal sols;

(3), three kinds of colloidal sols that will obtain carry out drying, obtain three kinds of xerogel;

(4), after the three kinds of xerogel pre-burnings that will obtain respectively, thermal treatment, obtain Na-β " Al ₂O ₃Three kinds of precursor powders, i.e. Na of solid electrolyte ₂O5Al ₂O ₃, Li ₂O5Al ₂O ₃Or MgO5Al ₂O ₃, BaO5Al ₂O ₃

(5), according to chemical formula (1-3x) Na of target product ₂O2xMgOxBaO5Al ₂O ₃Or (1-3x) Na ₂O2x Li ₂OxBaO5Al ₂O ₃The metallic element stoichiometric ratio, wherein 0.02＜x＜0.1 takes by weighing respectively precursor powder, preparation precursor powder mixture;

(6), described precursor powder mixture is added solvent, plastic agent and binding agent, through ball milling, obtain slurry;

(7), with the slurry granulation that obtains, hydrostatic profile is made biscuit;

(8), the biscuit of making is burnt till, then quench, naturally cool to room temperature, obtain the Na-β " Al of doping Ba ion ₂O ₃The solid electrolyte finished product.

2. method according to claim 1 is characterized in that, in described step (1), the salt of described sodium Metal 99.5, aluminium, lithium or magnesium and barium is soluble inorganic salt and/or solubility organic salt; Described solvent is deionized water and/or low-carbon alcohol; The volumetric molar concentration of obtain solution is 0.2-1mol/L.

3. method according to claim 2 is characterized in that, the soluble salt of aluminium is selected from Al (NO ₃) ₃9H ₂O, aluminum triacetate, aluminium triformate or their mixture; The soluble salt of sodium is selected from SODIUMNITRATE, sodium acetate, sodium oxalate or their mixture; The soluble salt of lithium is selected from lithium nitrate, lithium acetate, lithium oxalate or their mixture; The soluble salt of barium is selected from nitrate of baryta, barium acetate, barium oxalate or their mixture; The soluble salt of magnesium is selected from magnesium nitrate, magnesium acetate, magnesium oxalate or their mixture; Low-carbon alcohol as solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol or their mixture.

4. method according to claim 1 is characterized in that, in described step (2), described complexing agent is selected from the organic acid complexing agent; Described dispersion agent is ethoxy compound and/or ethylene oxide based compound; Described pH value conditioning agent is ammoniacal liquor and/or organic amine compound, and regulating the pH scope is between the 1-7; The ratio of all metallic cation mole numbers is 1 in the addition of described complexing agent and the solution: (1-3); The addition of described dispersion agent is the 0.2-3wt% of all metal-salt sums in the solution; The temperature rise rate of reacting by heating process was 10-15 ℃/minute, 50-70 ℃ of insulation 1-2 hour.

5. method according to claim 4 is characterized in that, described organic acid complexing agent is selected from EDTA, Thiovanic acid, citric acid, tartrate, oxalic acid, lactic acid or their mixture; Ethoxy compound as dispersion agent is alkylphenol polyoxyethylene, and the ethylene oxide based compound is polyoxyethylene; Organic amine compound as pH adjusting agent is selected from quadrol, trolamine or their mixture.

6. method according to claim 5 is characterized in that, described alkylphenol polyoxyethylene is selected from C5-C10 alkylphenol polyoxyethylene or their mixture, and wherein the number of ethylene oxide unit is 50-100; The molecular weight ranges of described polyoxyethylene is 400-1000 ten thousand dalton.

7. method according to claim 6 is characterized in that, the number of described ethylene oxide unit is 50-60; The molecular weight ranges of described polyoxyethylene is 400-600 ten thousand dalton.

8. method according to claim 1 is characterized in that, is 5-10 ℃/minute at the temperature rise rate of the drying process of described step (3), 80-120 ℃ of insulation 4-6 hour.

9. method according to claim 1 is characterized in that, the xerogel pre-burning process in described step (4), and temperature rise rate is 3-5 ℃/minute, respectively 150-200 ℃, 600-800 ℃ insulation 1-2 hour; Heat treatment process, temperature rise rate were 3-5 ℃/minute, 1000-1250 ℃ of insulation 1-2 hour.

10. method according to claim 1 is characterized in that, in the described step (6), described solvent is selected from ethanol, propyl alcohol, Virahol, ethylene dichloride, trichloroethane or their mixture; Described plastic agent is selected from ethylene glycol, polyoxyethylene glycol, dibutyl phthalate or their mixture; Described binding agent is selected from polyvinyl butyral acetal, polymethyl acrylate, ethyl cellulose or their mixture; The weight ratio of the addition of solvent and described precursor powder mixture is (1.5-4): 1; Described content of binder is the 3-10wt% of described precursor powder mixture; The weight ratio of described plastic agent and binding agent is (1-5): 1; Ball-milling Time is 4-6h.

11. method according to claim 1 is characterized in that, the temperature of the granulation process in described step (7) is 120-200 ℃; The pressure-controlling of hydrostatic profile process is at 300-350MPa.

12. method according to claim 1 is characterized in that, the temperature rise rate of the sintering process in described step (8) is 2-3 ℃/minute, and respectively 1400-1500 ℃ of insulation 1-2 hour, 1580-1620 ℃ is incubated 0.2-0.5 hour; The rate of temperature fall of quenching process was 2-3 ℃/minute, 1400-1500 ℃ of insulation 1-2 hour.

13. the Na-β " Al by the doping Ba ion of each described method preparation among the claim 1-12 ₂O ₃Solid electrolyte.