CN101941835A - Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same - Google Patents

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

Info

Publication number
CN101941835A
CN101941835A CN2010102860610A CN201010286061A CN101941835A CN 101941835 A CN101941835 A CN 101941835A CN 2010102860610 A CN2010102860610 A CN 2010102860610A CN 201010286061 A CN201010286061 A CN 201010286061A CN 101941835 A CN101941835 A CN 101941835A
Authority
CN
China
Prior art keywords
solid electrolyte
mixture
agent
kinds
minute
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102860610A
Other languages
Chinese (zh)
Other versions
CN101941835B (en
Inventor
张冰青
张祎晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN2010102860610A priority Critical patent/CN101941835B/en
Publication of CN101941835A publication Critical patent/CN101941835A/en
Application granted granted Critical
Publication of CN101941835B publication Critical patent/CN101941835B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Secondary Cells (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

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 a contiguous crystallographic site from a crystallographic site and realize conduction, 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 aluminium 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 is by Na +And O 2-The sodium oxygen layer of the fluff packing that ion constitutes 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 electrical conductivity is very low; And the sodium ion of debita spissitudo increases the BR vacancy concentration when occupying the BR position, and electrical conductivity increases.But because this lattice structure, 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-sulphur battery, sodium nickel chloride battery, the hot machine of sodium 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 history about 40 years just so far.Na-β " Al wherein 2O 3Solid electrolyte consists of the barrier film of sodium-sulphur battery, is the core material of sodium-sulphur battery.Sodium-sulfur cell has the following advantages: energy density is big, its theoretical specific energy (being the available point energy that battery unit mass or unit volume are had) is up to 760wh/kg, practical application can reach 390kw/kg, be four times of lithium cell, five times of nickel-based battery, ten times of lead-acid cell can be rated as state-of-the-art in the world 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; No self-discharge phenomenon adopts solid electrolyte, so do not adopt the sort of self-discharge and the side reaction of liquid electrolytic electrolitc secondary cell usually; The efficiency for charge-discharge height, enclosed pasture efficient is up to 100%; Volume is little, in light weight, automobile with one about one cubic metre, nearly weigh 300 kilograms high-power sodium-sulfur cell, promptly motor bus once charges and can travel more than 800 kilometer, car once charges and can exercise more than 1200 kilometer; Pollution-free, recyclable, manufacturing processed can not pollute environment, meets national new forms of energy standard fully, 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 a cell, and the cell maximum capacity that is used for energy storage reaches 650 ampere-hours, more than the power 120W; A plurality of cell combinations back is formed module, and 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 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 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, a kind of advanced energy-storage battery of potentialization 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 sodium sulphur energy-storage battery development in the world, development and the significant mechanism that uses.At present, a sodium-sulfur cell energy storage stands in global in service surplus the NGK existing 100.In July, 2004 formally puts into operation in Japan in maximum in the world NAs energy storage station (9.6Mw/57.6Mwh).The power at maximum sodium-sulfur battery energy storage station reaches 20Mw in the design, is the maximum electrochmical 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 to the direct converter of the thermoelectric energy of cycle fluid, it is the hot machine of sodium, conversion efficiency of thermoelectric can reach 30～40% in theory, the heat source temperature scope that is suitable for is 800～1200K, and be applicable to nuclear energy, the fossil energy, the thermal source of the various ways such as solar energy, 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 take place to β-Al 2O 3Mutually transformation, thereby electrical 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 part synthetic method, reaction sintering, spray drying process, sol-gal process, microwave sintering method, supercritical solvent seasoning etc. are arranged.
Chen Kun is firm etc., and " the part synthetic method prepares Na-β " Al 2O 3Pottery ", inorganic salts material journal, October in 1997, the 12nd the 5th phase of volume was adopted high-purity superfine alpha-Al 2O 3Powder, analytically pure sodium oxalate and lithium oxalate (or sodium carbonate and lithium carbonate) are made raw material, press earlier 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 3Powder is made secondary raw material with them then, presses Li 2Na-β " the Al that O is stable 2O 3Proportion of composing batching is made the medium ball milling with absolute alcohol, adds polyvinyl butyral as binding agent, drying, and granulating with the pressure isostatic compaction 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 26th the 1st phase of volume, aluminum nitrate, yellow soda ash and magnesium nitrate that operational analysis is pure, 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, and slow transpiring moisture is made gel under 80 ℃.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-gal process prepares Na-β " Al 2O 3The method of solid electrolyte precursor "; sodium nitrate aqueous solution, absolute ethyl 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; add then 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 superfine 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 stabilizing agent, the preparation precursor powder after granulation, moulding, is put into micro-wave oven with the precursor powder that makes, and Fast Sintering obtains Na-β " Al 2O 3Electrolyte.
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 component distributing.Na-β " Al 2O 3These performances of solid electrolyte depend on chemical composition 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 micro-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 electrical conductivity of solid electrolyte is so that the bigger effect of its performance.
On the other hand, barium ions 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 "-aluminium 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 ions, can increase the BR vacancy concentration, thereby improve Na-β " Al 2O 3The solid electrolyte electrical conductivity.
But above-mentioned research only limits to theoretical calculation stages.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 stabilizing agent, and the salt of containing metal barium is conditioning agent, adds respectively solvent, complexing agent, dispersant and pH value conditioning agent, make precursor powder, with precursor powder granulation, hydrostatic profile, make biscuit, burn till, quench then, 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 proportion, take by weighing respectively sodium metal and aluminium salt, take by weighing lithium metal 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, dispersant 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 heat 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 proportion, 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,, obtain slurry through ball milling;
7, with the slurry granulation that obtains, hydrostatic profile is made biscuit;
8, the biscuit of making is burnt till, quench then, 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 an alkylphenol polyoxyethylene, and the ethylene oxide based compound is polyoxyethylene (PEO); Organic amine compound in the pH regulator 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; The 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 good 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 electrical 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 electrical conductivity, and has significantly improved Na-β " Al 2O 3The service life of solid electrolyte.
Description of drawings
Fig. 1 is preparation Na-β " Al 2O 3The flow chart 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 following thermostatically heating, stirring form uniform solution.To wherein adding 25.36g citric acid (A.R) and 2.79g polyvinyl alcohol, continue heated and stirred then, formed wet gel through 6 hours gradually.The wet gel that obtains moved to 250 ℃ of oven dry obtain xerogel in the baking oven.Then gel was calcined 3 hours down at 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, cooling thereupon, 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 stabilizing agent, is Na according to intermediate objective product chemical formula 2O5Al 2O 3And Li 2O5Al 2O 3The metallic element stoichiometric proportion, 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 metal cation molal quantitys in complexing agent and each solution, add respectively C 6H 8O 7H 2O 135.5857 grams, 31.3868 grams, be the 1wt% of all slaine sums in the various solution by dispersant, add respectively polyethylene glycol oxide (PEO-600) 2.4737 grams, 0.5645 gram, regulate pH=3 with ethylenediamine respectively, and mix, heating 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 heating 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, heating 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 proportion, 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 resin (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, heating rate are 3 ℃/minute, respectively 1475 ℃ of insulations 2 hours, 1615 insulations 0.5 hour are quenched then, 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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and the various solution, add respectively polyethylene glycol oxide (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram, regulate pH=3 with ethylenediamine respectively, and mix, heating 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 heating 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, heating 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 proportion, 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 resin (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, heating rate are 3 ℃/minute, respectively 1475 ℃ of insulations 2 hours, 1615 insulations 0.5 hour are quenched then, 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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and the various solution, add respectively polyethylene glycol oxide (PEO-600) 0.4644 gram, 0.0710 gram, 0.0748 gram, regulate pH=7 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 6.9653 grams, 1.0644 grams, 1.1224 grams, regulate pH=1 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carrying out the pre-burning process then, is 5 ℃/minute with temperature rise rate, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, 1615 insulations 0.5 hour are quenched then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and the various solution, add respectively polyethylene glycol oxide (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram; Regulate pH=3 with ethylenediamine respectively; And mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, 1615 insulations 0.5 hour are quenched then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 2.3218 grams, 0.3548 gram, 0.3741 gram; Regulate pH=3 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 polyethylene glycol in the mixture of three kinds of precursor powders, remaining specific 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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram; Regulate pH=3 with ethylenediamine respectively; And mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 0.4937 gram, 0.1929 gram, 0.0855 gram, regulate pH=7 with ethylenediamine respectively, and mix, heating 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.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 7.4048 grams, 2.8930 grams, 1.2823 grams, regulate pH=1 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtain three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carry out the pre-burning process then, temperature rise rate is 5 ℃/minute, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and the three kinds of solution, add respectively polyethylene glycol oxide (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram, regulate pH=3 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carrying out the pre-burning process then, is 5 ℃/minute with temperature rise rate, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 stabilizing agent, 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 proportion, 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 metal cation molal quantitys 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 slaine sums in dispersant and each solution, add respectively polyethylene glycol oxide (PEO-600) 2.4683 grams, 0.9643 gram, 0.4274 gram, regulate pH=3 with ethylenediamine respectively, and mix, heating rate is 10 ℃/minute, 60 ℃ of insulations 1 hour, obtains three kinds of colloidal sols.With three kinds of colloidal sols that obtain, be 5 ℃/minute with temperature rise rate, carried out drying in 4 hours 100 ℃ of insulations, obtain three kinds of xerogel.Carrying out the pre-burning process then, is 5 ℃/minute with temperature rise rate, respectively 150 ℃, 700 ℃ insulations 2 hours.Heat-treat afterwards process, heating 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 proportion, 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 resin (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, quench then.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 as plastic agent and keep plastic agent and the weight ratio of binding agent is 3: 1 in the mixture of three kinds of precursor powders; The temperature rise rate of sintering process is 2 ℃/minute, and respectively 1455 ℃ of insulations 2 hours, 1595 ℃ are incubated 0.5 hour, quench then.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 conventional method of solid electrolyte, the electrical conductivity of the sample 1 ' that obtains and micro-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, obtain the actual density of sample according to the definition of density, based on theoretical density 3.26g/cm with drainage 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 (operating temperature of sodium-sulphur battery is generally 275 ℃-350 ℃) condition, measures with the V-A method, gets electrical conductivity by formula σ=1/ ρ;
Rupture strength is measured and is adopted conventional known line-of-sight course (YS/T 63.14-2006) to measure;
Na-β " Al 2O 3Solid electrolyte is made the electron probe sample of δ 1.8 * 3 * 4mm, test at EPMA8705QH, experimental condition is as follows: carried out the electron probe experiment under electric current 50nA, accelerating potential 20kV, the beam spot diameter 1 μ m, measured the bombardment time that micro-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
Figure BSA00000276154100211
By last table 1 as seen: 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 superfine 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 of precursor powder figure as shown in Figure 2, by the prepared Li of embodiment 1 2O5AL 2O 3The XRD of precursor powder figure as shown in Figure 3, by the prepared BaO5AL of embodiment 1 2O 3The XRD of precursor powder precursor powder figure 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 crystallite dimension is about 1-3 μ m, and structure is comparatively fine and close, has therefore obtained higher relative density and rupture 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 electrical conductivity of solid electrolyte, its degenerate problem have also obtained the improvement of quite big degree.Therefore, the product that adopts method of the present invention to obtain has broad application prospects.
By above-mentioned all embodiment as can be seen, in concrete implementation process, those skilled in the art can both carry out concrete enforcement according to the specialized range of each processing parameter, does not exceed with the given the foregoing description 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 (12)

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 stabilizing agent, 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 proportion, take by weighing respectively sodium metal and aluminium salt, take by weighing lithium metal 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, dispersant 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, heat 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 2O2xLi 2OxBaO5Al 2O 3The metallic element stoichiometric proportion, 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, quench then, 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 configuration 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 an alkylphenol polyoxyethylene, and the ethylene oxide based compound is a polyoxyethylene; Organic amine compound as the pH regulator 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, preferred 50-60; The molecular weight ranges of described polyoxyethylene is 400-1000 ten thousand dalton, preferred 400-600 ten thousand dalton.
7. 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.
8. 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.
9. 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; The ball milling time is 4-6h.
10. 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.
11. 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.
12. the Na-β " Al by the doping Ba ion of each described method preparation among the claim 1-11 2O 3Solid electrolyte.
CN2010102860610A 2010-09-15 2010-09-15 Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same Expired - Fee Related CN101941835B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010102860610A CN101941835B (en) 2010-09-15 2010-09-15 Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102860610A CN101941835B (en) 2010-09-15 2010-09-15 Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same

Publications (2)

Publication Number Publication Date
CN101941835A true CN101941835A (en) 2011-01-12
CN101941835B CN101941835B (en) 2013-01-16

Family

ID=43434074

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102860610A Expired - Fee Related CN101941835B (en) 2010-09-15 2010-09-15 Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same

Country Status (1)

Country Link
CN (1) CN101941835B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098118A (en) * 2013-04-15 2014-10-15 成都慧成科技有限责任公司 Preparation method for high-ion-flux beta''-Al2O3 precusor powder
CN104143661A (en) * 2014-07-31 2014-11-12 南京工业大学 High-strength beta-Al203 solid electrolyte preparation method
CN104276816A (en) * 2013-07-12 2015-01-14 中国科学院上海硅酸盐研究所 Method for preparing sodium battery electrolyte membrane by employing spray deposition molding
CN104556980A (en) * 2013-10-16 2015-04-29 中国科学院上海硅酸盐研究所 Method for preparing beta-Al2O3 ceramic electrolyte separator for sodium battery
CN106803601A (en) * 2017-02-26 2017-06-06 合肥国轩高科动力能源有限公司 A kind of preparation method of solid electrolyte lithium lanthanum titanium oxide film
US10199682B2 (en) * 2011-06-29 2019-02-05 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US10601074B2 (en) 2011-06-29 2020-03-24 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US10658705B2 (en) 2018-03-07 2020-05-19 Space Charge, LLC Thin-film solid-state energy storage devices
US11527774B2 (en) 2011-06-29 2022-12-13 Space Charge, LLC Electrochemical energy storage devices

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2283237A (en) * 1993-10-29 1995-05-03 Programme 3 Patent Holdings B-alumina compound
CN101717259A (en) * 2009-12-22 2010-06-02 中国科学院过程工程研究所 Method for preparing Na-beta'-Al2O3 solid electrolyte precursor by adopting sol-gel method
CN101734911A (en) * 2009-12-22 2010-06-16 南京工业大学 Preparation method of Na-beta''-Al2O3 solid electrolyte

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2283237A (en) * 1993-10-29 1995-05-03 Programme 3 Patent Holdings B-alumina compound
CN101717259A (en) * 2009-12-22 2010-06-02 中国科学院过程工程研究所 Method for preparing Na-beta'-Al2O3 solid electrolyte precursor by adopting sol-gel method
CN101734911A (en) * 2009-12-22 2010-06-16 南京工业大学 Preparation method of Na-beta''-Al2O3 solid electrolyte

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《Journal of Materials Science》 19881231 Yin Sheng et al. The Mechanical and Electrical-Properties of ZrO2-Nabeta"-Al2O3 Composites 958-967 1-12 , 第23期 *
《Journal of Solid State Chemistry》 19851231 ALEXANDER PECHENIK et al. Divalent and Mixed Divalent/Monovalent Conduction in beta"- Alumina: A Monte Carlo Study 103-113 1-12 第58卷, *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11527774B2 (en) 2011-06-29 2022-12-13 Space Charge, LLC Electrochemical energy storage devices
US10601074B2 (en) 2011-06-29 2020-03-24 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US10199682B2 (en) * 2011-06-29 2019-02-05 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
CN104098118A (en) * 2013-04-15 2014-10-15 成都慧成科技有限责任公司 Preparation method for high-ion-flux beta''-Al2O3 precusor powder
CN104276816A (en) * 2013-07-12 2015-01-14 中国科学院上海硅酸盐研究所 Method for preparing sodium battery electrolyte membrane by employing spray deposition molding
CN104276816B (en) * 2013-07-12 2016-08-10 中国科学院上海硅酸盐研究所 The method of sode cell electrolyte membrance is prepared in sprayed deposit molding
CN104556980B (en) * 2013-10-16 2016-09-07 中国科学院上海硅酸盐研究所 One prepares sode cell beta-Al2o3the method of ceramic electrolyte barrier film
CN104556980A (en) * 2013-10-16 2015-04-29 中国科学院上海硅酸盐研究所 Method for preparing beta-Al2O3 ceramic electrolyte separator for sodium battery
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
CN104143661A (en) * 2014-07-31 2014-11-12 南京工业大学 High-strength beta-Al203 solid electrolyte preparation method
CN106803601A (en) * 2017-02-26 2017-06-06 合肥国轩高科动力能源有限公司 A kind of preparation method of solid electrolyte lithium lanthanum titanium oxide film
CN106803601B (en) * 2017-02-26 2019-12-13 合肥国轩高科动力能源有限公司 preparation method of solid electrolyte lithium lanthanum titanium oxide film
US10658705B2 (en) 2018-03-07 2020-05-19 Space Charge, LLC Thin-film solid-state energy storage devices

Also Published As

Publication number Publication date
CN101941835B (en) 2013-01-16

Similar Documents

Publication Publication Date Title
CN101941835B (en) Preparation method of Ba ion doped Na-beta'-Al2O3 solid electrolyte and solid electrolyte prepared by using same
CN100579899C (en) Method of producing lithium iron phosphate with high compacted density and excellent adhesive property
CN101734637B (en) Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery
CN101734911B (en) Preparation method of Na-beta''-Al2O3 solid electrolyte
CN101339995A (en) Preparation of lithium iron phosphate positive electrode material for lithium ion power cell
CN105428648B (en) A kind of preparation method of battery anode material of lithium iron phosphate
CN105845974A (en) Preparation method for positive electrode material NaFePO4/C of sodium ion battery
CN102088074A (en) Anode material of composite silicate and preparation method thereof
CN106450214B (en) Layered lithium iron phosphate composite material and preparation method thereof
CN101997118A (en) Lithium ferric manganese phosphate as cathode material of lithium ion battery and preparation method thereof
CN102097616A (en) Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder
CN103531849A (en) Sulfide electrolyte materials, preparation method thereof and all-solid lithium secondary battery
CN103618065B (en) LiFePO 4 material and preparation method thereof
CN110085810B (en) Preparation method and application of coated modified lithium cobaltate positive electrode material
CN103224226A (en) Nano-lithium iron phosphate material suitable for high rate power battery and preparation method thereof
CN101841039A (en) Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof
JP2023548993A (en) Method for producing high-rate lithium iron phosphate cathode material
CN102208624A (en) Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method
CN101369661A (en) Sodium-base lithium ion secondary battery anode material and method of manufacturing the same
CN114105115B (en) Production method and application of ferric phosphate and lithium iron phosphate
CN101262059B (en) A method for making anode material LiFePO4 of lithium ion battery
CN101850957A (en) Method for preparing nano-lithium iron phosphate of cathode material of lithium ion battery
CN108735995B (en) Composite material, preparation method, battery positive electrode material and battery
CN101445229B (en) A colloidal sols- jelly glue method for preparing lithium vanadium phosphate lithium ion battery positive pole material adulterating titanium
CN103117391A (en) Preparation method of molybdenum-doped carbon-coated lithium iron phosphate, namely positive electrode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130116

Termination date: 20150915

EXPY Termination of patent right or utility model