CN104143661B - A kind of high intensity beta-Al2o3method for preparing solid electrolyte - Google Patents
A kind of high intensity beta-Al2o3method for preparing solid electrolyte Download PDFInfo
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Abstract
The present invention relates to a kind of high intensity beta Al2O3Method for preparing solid electrolyte, it concretely comprises the following steps: the salt containing transition metal atoms adds in the oxide of sodium salt, lithium salts and aluminium salt or aluminum, and after mixing, ball milling is dried, and after sieving, pre-burned obtains forerunner's material；Forerunner is expected, and powder ball milling is dried, adds PVA aqueous solution after sieving and expect in powder to forerunner and mix homogeneously, compressing；C then the biscuit of molding is put into and is slowly heated to 550 650 DEG C of insulations by (), then heat up, and in 1,550 1680 DEG C of heat preservation sinterings, is then cooled to 1,400 1500 DEG C of insulations, and last furnace cooling obtains the beta Al of high intensity2O3The sintered body of solid electrolyte.The present invention adds transition metal atoms and uses solid phase method to prepare, and step is simple, low cost, it is adaptable to produce in enormous quantities, is ensureing beta Al2O3Improve again its consistency and mechanical strength when of the electrical conductivity of electrolyte, improve ionic conductivity.
Description
Technical field
The present invention relates to the technology of preparing of the solid electrolyte of sodium-sulphur battery, it is provided that a kind of high intensity beta-Al2O3
Method for preparing solid electrolyte, belongs to the preparation field of energy and material.
Background technology
Sodium sulfur (NaS) battery is a kind of high-temperature solid electrolytic cell, and operating temperature is 300-350 DEG C, with molten state
Elemental sulfur and metallic sodium are respectively as the both positive and negative polarity of battery, with beta-Al2O3As electrolyte and barrier film.It has energy storage density
The advantages such as greatly, efficiency is high, operating cost is low, maintenance is easier to, free from environmental pollution, length in service life.NaS battery energy storage system is certainly
Since 2002 realize commercial operations, obtain at aspects such as load control, power stability, the quality of power supply, DC back-up power supplies
To extensively application.Beta-Al2O3Solid electrolyte includes β "-Al2O3With β-Al2O3, β " is altogether with β phase mutually as a rule
Deposit.Wherein, polycrystal Beta "-Al2O3Electrical conductivity be β-Al2O33-4 times of electrical conductivity.Therefore, " content of phase contributes to improve β
Improve beta-Al2O3The electrical conductivity of electrolyte.But, β "-Al under high temperature2O3Easily to β-Al2O3Change, become under electrical conductivity
The key factor of fall.And Na in sintering process2The volatilization of O makes again the performance of electrolyte goods there is unstability.Meanwhile,
beta-Al2O3Easily the C axle along crystal ftractures, and metallic sodium there will be depositional phenomenon in the lattice or crystal boundary of electrolyte so that
Electrolyte turns black and ruptures, and causes sodium-sulphur battery to lose efficacy.Simultaneously because the requirement of NaS battery be Na and S all in liquid,
And reach the high temperature of about 300 DEG C, once ceramic dielectric is damaged, and liquid Na of high temperature will directly contact with S and play occurs
Strong exothermic reaction, consequence can be hardly imaginable, so the raising of ceramic dielectric mechanical performance is most important.Because high intensity,
High density and high conductivity are obtained in that specific energy height, Na-the β "-Al of length in service life2O3Solid electrolyte.The most both at home and abroad
There is the researcher of many at preparation beta-Al2O3Ti is added during electrolyte4+、Zr4+Deng metal ion so that the beta-obtained
Al2O3The combination property of electrolyte all improves；But the Ti added4+、Zr4+More expensive Deng metal ion, volume of production is little.
Summary of the invention
The purpose of this invention is to provide a kind of high intensity beta-Al to improve the deficiencies in the prior art2O3Solid electricity
Solve the preparation method of matter.
The present invention is achieved through the following technical solutions:
A kind of high intensity beta-Al2O3Method for preparing solid electrolyte, it concretely comprises the following steps: (a) is former containing transition metal
The salt of son adds in the oxide of sodium salt, lithium salts and aluminium salt or aluminum, is expert at anhydrous organic polar solvent for medium after mixing
In celestial body grinding machine, ball milling is dried, and obtains forerunner's material by batch-type furnace pre-burned after sieving；B forerunner is expected that powder is in anhydrous polar organic by ()
Solvent is dried after ball milling, adds PVA aqueous solution after sieving and expect in powder to forerunner and mix homogeneously, compressing；C () then
The biscuit of molding is put into and box Si-Mo rod stove is slowly heated to 550-650 DEG C of insulation carries out defat, then heat up, and in
1550-1680 DEG C of heat preservation sintering, is then cooled to 1400-1500 DEG C of insulation, and last furnace cooling obtains the beta-of high intensity
Al2O3The sintered body of solid electrolyte.
The preferably described salt containing transition metal atoms is the oxalates containing transition metal atoms, nitrate, carbonate, vinegar
Hydrochlorate, citrate or formates, wherein transition metal atoms is Fe, Cr or Ni.Preferably described sodium salt, lithium salts and aluminium salt are divided
Wei the oxalates of sodium, nitrate, carbonate, acetate, citrate or formates, the oxalates of lithium, nitrate, carbonic acid
Salt, acetate, citrate or formates, the oxalates of aluminum, nitrate, carbonate, acetate, citrate or formates.
The preferably addition of the salt containing transition metal atoms is: the oxide containing transition metal atoms accounts for total oxide quality
0.005-0.75%；The addition of sodium salt is Na2O accounts for the 10.60-10.80% of total oxide quality；The addition of lithium salts is for accounting for
The 0.40-1.00% of total oxide quality；Remaining is Al2O3；Wherein total oxide is the oxygen of sodium salt, lithium salts and aluminium salt or aluminum
Li in compound2O、Na2O、Al2O3Gross mass with transition metal atoms oxide；Most preferably Na2O and Al2O3Mol ratio be 1:
About 5.
In preferred steps (a) and (b), Ball-milling Time is 6-12 hour；Pressure compressing in step (b) is 10-
30MPa。
Calcined temperature described in preferred steps (a) is 1000-1300 DEG C, and burn-in time is 1-3 hour；In step (c)
The speed being slowly heated is 1-3 DEG C/min, is slowly heated to insulation 1-3 hour when 550-650 DEG C；Burn in 1550-1680 insulation
Knot 5-25min；Being cooled to the rate of temperature fall when 1400-1500 DEG C is 2-3 DEG C/min, is cooled to insulation when 1400-1500 DEG C
40-80min。
Anhydrous organic polar solvent described in preferred steps (a) and (b) is dehydrated alcohol, absolute ether or anhydrous third
One in ketone.
The solution that preferably described PVA aqueous solution is polyvinyl alcohol and deionized water is prepared for 5-10:100 in mass ratio；
The addition of PVA aqueous solution is the 5-15% that forerunner expects powder quality.
X-ray is used to carry out beta-Al2O3The structural analysis of solid electrolyte；Scanning electron microscope is used to carry out morphology analysis；
According to Archimedes principle, carry out body density measurement by hydrostatic weight method；Use line-of-sight course test bending strength；Use
Ac impedance technology testing conductivity.
Beneficial effect:
Due to the abundant raw material of transition metal atoms, and the metal ion added than current numerous researcheres is (such as Ti4+、
Zr4+Deng) price is cheaper, advantageously reduces preparation cost.Additionally, the preparation process of the present invention is simple, use solid phase legal system
Standby, it is adaptable to produce in enormous quantities.Meanwhile, present invention employs the preparation technology of interpolation transition metal atoms to make beta-Al2O3
The intensity of solid electrolyte improves 10-55%, can improve its consistency simultaneously, reduces grain boundary resistance, improves ionic conduction
Property, ensureing beta-Al2O3Its consistency and mechanical strength is improved again the when of the electrical conductivity of electrolyte.
Accompanying drawing explanation
Fig. 1 is comparative example of the present invention, embodiment 1, embodiment 2 and the XRD figure of embodiment 3 product；
Fig. 2 is the SEM figure of comparative example product of the present invention；
Fig. 3 is the SEM figure of the embodiment of the present invention 4 product；
Fig. 4 is the AC impedance spectrogram at different temperatures of the embodiment of the present invention 2 product.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is described in further detail, but embodiments of the present invention do not limit
In this.
Comparative example:
Weigh Disodium oxalate. (A.R.) 6.9815g (Na2O:10.76 wt%), aluminium oxide (VK-L30) 26.5716g, carbonic acid
Lithium (A.R.) 0.5193g (Li2O:0.7 wt%), with dehydrated alcohol for medium ball milling 8 hours in planetary ball mill after mixing
And be dried, prepare forerunner's material with batch-type furnace at 1250 DEG C of pre-burning 2h after sieving.Forerunner is expected, and powder ball milling 8 in dehydrated alcohol is little
Time be dried, after sieving add forerunner expect powder quality 10% PVA aqueous solution (polyvinyl alcohol and deionized water quality ratio are 5:
100) expecting mix homogeneously in powder to forerunner, compressing under 20MPa is circular and cuboid sheet.Biscuit is put into box
Si-Mo rod stove is slowly heated (1 DEG C/min) and carries out defat to 600 DEG C of insulation 2h, then heat up, and in 1600 DEG C of heat preservation sinterings
10min, then cooling (2 DEG C/min) is incubated 60min at 1450 DEG C, and furnace cooling obtains sintered body, is finally entered by sintered body
The various performance tests of row.As shown in 0wt% in Fig. 1 XRD, test obtains now β "-Al2O3The content of phase is 94.68%, Fig. 2
Being the profile scanning electron microscopic picture of gained sample, obtained the sintered body of densification, the bulk density of sintered body is 3.1598g/
cm3, the bending strength of cuboid sheet is 172.6MPa.
Embodiment 1:
Weigh Disodium oxalate. (A.R.) 6.9702g (Na2O:10.75 wt%), aluminium oxide (VK-L30) 26.5282g, carbonic acid
Lithium (A.R.) 0.5193g (Li2O:0.7 wt%), Fe(NO3)39H2O (A.R.) 0.1894g (Fe2O30.15 wt%), mixing
After with absolute ether for medium ball milling 7 hours being dried in planetary ball mill, with batch-type furnace at 1100 DEG C of pre-burning 2h after sieving
Prepare forerunner's material.Forerunner is expected, and powder ball milling in absolute ether is dried for 7 hours, adds forerunner after sieving and expect powder quality
The PVA aqueous solution of 5% (polyvinyl alcohol and deionized water quality than for 10:100) expects mix homogeneously in powder to forerunner,
Compressing under 10MPa is circular and cuboid sheet.Biscuit is put in box Si-Mo rod stove and be slowly heated (2 DEG C/min) extremely
650 DEG C of insulation 1h carry out defat, then heat up, and in 1600 DEG C of heat preservation sintering 15min, then cooling (3 DEG C/min) extremely exists
1450 DEG C of insulation 60min, furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Such as Fe in Fig. 1 XRD
Shown in 0.15wt%, test obtains now β "-Al2O3The content of phase is 95.96%, and the bulk density of sintered body disk is
3.1801g/cm3, bending strength is to improve 52% compared to comparative example.
Embodiment 2:
Weigh sal soda (A.R.) 14.9397g (Na2O:10.80 wt%), aluminium oxide (VK-L30)
26.6516g, lithium oxalate (A.R.) 0.3840g (Li2O:0.4 wt%), nickel oxalate (A.R.) 0.0006g (NiO 0.01
Wt%), with dehydrated alcohol for medium ball milling 9 hours being dried in planetary ball mill after mixing, exist with batch-type furnace after sieving
1300 DEG C of pre-burning 1h prepare forerunner's material.Forerunner is expected, and powder ball milling in dehydrated alcohol is dried for 9 hours, after sieving, adds forerunner's material
To forerunner, the PVA aqueous solution of the 7% of powder quality (polyvinyl alcohol and deionized water quality than for 7:100) expects that in powder, mixing is all
Even, compressing under 15MPa is circular and cuboid sheet.Biscuit is put in box Si-Mo rod stove and be slowly heated (1.5
DEG C/min) and carry out defat to 550 DEG C of insulation 3h, then heat up, and in 1580 DEG C of heat preservation sintering 15min, then cooling (2 DEG C/
Min) being incubated 80min at 1400 DEG C, furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Such as figure
In 1XRD shown in Ni 0.01wt%, test obtains now β "-Al2O3The content of phase is 98.14%, and the volume of sintered body disk is close
Degree is 3.1716g/cm3, bending strength improves 13% compared to comparative example, and Fig. 4 is sample exchange resistance at different temperatures
Anti-spectrogram, along with the liter high conductivity of temperature is to increase.
Embodiment 3:
Weigh Disodium oxalate. (A.R.) 7.0026g (Na2O:10.80 wt%), ANN aluminium nitrate nonahydrate (A.R.) 97.9839g,
Lithium carbonate (A.R.) 0.2960g (Li2O:0.4 wt%), nickel nitrate hexahydrate (A.R.) 0.0006g (NiO 0.005wt%),
With dehydrated alcohol for medium ball milling 11 hours being dried in planetary ball mill after mixing, pre-at 1000 DEG C with batch-type furnace after sieving
Burn 2h and prepare forerunner's material.Forerunner is expected, and powder ball milling in dehydrated alcohol is dried for 11 hours, adds forerunner after sieving and expect powder matter
The PVA aqueous solution of the 10% of amount (polyvinyl alcohol and deionized water quality than for 5:100) expects mix homogeneously in powder to forerunner,
Compressing under 25MPa is circular and cuboid sheet.Biscuit is put in box Si-Mo rod stove and be slowly heated (3 DEG C/min) extremely
620 DEG C of insulation 2h carry out defat, then heat up, and in 1560 DEG C of heat preservation sintering 25min, then cooling (3 DEG C/min) extremely exists
1400 DEG C of insulation 70min, furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Test obtains now
β"-Al2O3The content of phase is 97.20%, and the bulk density of sintered body disk is 3.1632/cm3, bending strength is compared to contrast
Example improves 11%.
Embodiment 4:
Weigh sodium nitrate (A.R.) 4.3960g (Na2O:10.69 wt%), ANN aluminium nitrate nonahydrate (A.R.) 96.9699g,
Lithium nitrate (A.R.) 0.6210g (Li2O:0.9wt%), nickel nitrate hexahydrate (A.R.) 05840g (NiO 0.5 wt%), mixing
After with dehydrated alcohol for medium ball milling 10 hours being dried in planetary ball mill, with batch-type furnace at 1300 DEG C of pre-burning 2h after sieving
Prepare forerunner's material.Forerunner is expected, and powder ball milling in dehydrated alcohol is dried for 10 hours, adds forerunner after sieving and expect powder quality
The PVA aqueous solution of 15% (polyvinyl alcohol and deionized water quality than for 5:100) expects mix homogeneously in powder to forerunner,
Compressing under 30MPa is circular and cuboid sheet.Biscuit is put in box Si-Mo rod stove and be slowly heated (2 DEG C/min) extremely
600 DEG C of insulation 2h carry out defat, then heat up, and in 1580 DEG C of heat preservation sintering 20min, then cooling (2 DEG C/min) extremely exists
1450 DEG C of insulation 70min, furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Test obtains now
β"-Al2O3The content of phase is 99.00%, and the bulk density of sintered body disk is 3.1748g/cm3, bending strength is compared to contrast
Example improves 11%.
Embodiment 5:
Weigh sodium nitrate (A.R.) 4.4249 (Na2O:10.76wt%), aluminium oxide (VK-L30) 26.5497g, lithium carbonate
(A.R.)0.5193g(Li2O:0.7 wt%), chromic nitrate (A.R.) 0.0235g (Cr2O30.05 wt%), with anhydrous after mixing
Ethanol is medium ball milling 6 hours being dried in planetary ball mill, prepares forerunner with batch-type furnace at 1050 DEG C of pre-burning 2h after sieving
Material.Forerunner is expected, and powder ball milling in dehydrated alcohol is dried for 6 hours, after sieving, adds the PVA that forerunner expects the 10% of powder quality
Aqueous solution (polyvinyl alcohol and deionized water quality than for 8:100) expects mix homogeneously in powder to forerunner, is pressed under 30MPa
Type is circular and cuboid sheet.Biscuit is put into box Si-Mo rod stove is slowly heated (3 DEG C/min) to 600 DEG C insulation 2h enter
Row defat, then heats up, and in 1680 DEG C of heat preservation sintering 5min, then cooling (2 DEG C/min) is incubated 40min at 1500 DEG C,
Furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Test obtains now β "-Al2O3The content of phase is
96.83%, Fig. 4 are the profile scanning electron microscopic picture of gained sample, observe it appeared that crystal grain now is than the size of embodiment
Evenly, finer and close, the bulk density of sintered body disk is 3.1787g/cm3, bending strength improves compared to comparative example
24%.
Embodiment 6:
Weigh Disodium oxalate. (A.R.) 6.9547g (Na2O:10.72wt%), ANN aluminium nitrate nonahydrate (A.R.) 97.3141g, carbon
Acid lithium (A.R.) 0.5193g (Li2O:0.8wt%), chromic nitrate (A.R.) 0.1174g (Cr2O30.25 wt%), after mixing with
Dehydrated alcohol is medium ball milling 8 hours being dried in planetary ball mill, prepares at 1150 DEG C of pre-burning 2h with batch-type furnace after sieving
Forerunner expects.Forerunner expecting, powder ball milling in dehydrated alcohol is dried for 8 hours, and after sieving, interpolation forerunner expects the 10% of powder quality
PVA aqueous solution (polyvinyl alcohol and deionized water quality than for 5:100) expects mix homogeneously in powder to forerunner, presses under 25MPa
System is shaped to circular and cuboid sheet.Biscuit is put into and box Si-Mo rod stove is slowly heated (1 DEG C/min) to 600 DEG C of insulations
2h carries out defat, then heats up, and in 1620 DEG C of heat preservation sintering 10min, then cooling (2 DEG C/min) is to 1450 DEG C of insulations
60min, furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Test obtains now β "-Al2O3Phase
Content is 97.71%, and the bulk density of sintered body disk is 3.1761g/cm3, bending strength improves compared to comparative example
27%.
Embodiment 7:
Weigh sodium nitrate (A.R.) 4.3804g (Na2O:10.65 wt%), aluminium oxide (VK-L30) 26.2815g, oxalic acid
Lithium (A.R.) 0.9600g (Li2O:1 wt%), chromic nitrate (A.R.) 0.3523g (Cr2O30.75 wt%), with anhydrous after mixing
Acetone is medium ball milling 9 hours being dried in planetary ball mill, prepares forerunner with batch-type furnace at 1250 DEG C of pre-burning 2h after sieving
Material.Forerunner is expected, and powder ball milling in anhydrous propanone is dried for 9 hours, after sieving, adds the PVA that forerunner expects the 10% of powder quality
Aqueous solution (polyvinyl alcohol and deionized water quality than for 5:100) expects mix homogeneously in powder to forerunner, is pressed under 20MPa
Type is circular and cuboid sheet.Biscuit is put into box Si-Mo rod stove is slowly heated (1 DEG C/min) to 600 DEG C insulation 2h enter
Row defat, then heats up, and in 1600 DEG C of heat preservation sintering 10min, then cooling (2 DEG C/min) is incubated 80min at 1450 DEG C,
Furnace cooling obtains sintered body, finally sintered body is carried out various performance test.Test obtains now β "-Al2O3The content of phase is
98.00%, the bulk density of sintered body disk is 3.2001g/cm3, bending strength improves 21% compared to comparative example.
Claims (7)
1. high intensity beta-Al2O3Method for preparing solid electrolyte, it concretely comprises the following steps: (a) contains transition metal atoms
Salt add in the oxide of sodium salt, lithium salts and aluminium salt or aluminum, do with anhydrous organic polar solvent for medium ball milling after mixing
Dry, pre-burned of sieving obtains forerunner's material；B forerunner is expected that powder is dried after ball milling in anhydrous organic polar solvent by (), add after sieving
Add PVA aqueous solution and expect in powder to forerunner and mix homogeneously, compressing；C then the biscuit of molding is slowly heated to by ()
550-650 DEG C of insulation, then heats up, and in 1550-1680 DEG C of heat preservation sintering, is then cooled to 1400-1500 DEG C of insulation,
Rear furnace cooling obtains the beta-Al of high intensity2O3Solid electrolyte；Wherein transition metal atoms is Fe, Cr or Ni；Containing transition
The addition of the salt of metallic atom is: the oxide containing transition metal atoms accounts for the 0.005-0.75% of total oxide quality；Sodium salt
Addition be Na2O accounts for the 10.60-10.80% of total oxide quality；The addition of lithium salts is Li2O accounts for total oxide quality
0.40-1.00%；Wherein total oxide be sodium salt, lithium salts and aluminium salt or aluminum oxide in Li2O、Na2O、Al2O3With transition gold
Belong to the gross mass of elemental oxygen compound.
Preparation method the most according to claim 1, it is characterised in that: the described salt containing transition metal atoms is containing transition
The oxalates of metallic atom, nitrate, carbonate, acetate, citrate or formates.
Preparation method the most according to claim 1, it is characterised in that: described sodium salt, lithium salts and aluminium salt are respectively sodium
Oxalates, nitrate, carbonate, acetate, citrate or formates, the oxalates of lithium, nitrate, carbonate, acetate,
Citrate or formates, the oxalates of aluminum, nitrate, carbonate, acetate, citrate or formates.
Preparation method the most according to claim 1, it is characterised in that it is little that step (a) and Ball-milling Time in (b) are 6-12
Time；Pressure compressing in step (b) is 10-30MPa.
Preparation method the most according to claim 1, it is characterised in that the calcined temperature described in step (a) is 1000-
1300 DEG C, burn-in time is 1-3 hour；The speed being slowly heated in step (c) is 1-3 DEG C/min, is slowly heated to 550-650
DEG C time insulation 1-3 hour；At 1550-1680 heat preservation sintering 5-25min；Being cooled to the rate of temperature fall when 1400-1500 DEG C is
2-3 DEG C/min, it is cooled to insulation 40-80min when 1400-1500 DEG C.
Preparation method the most according to claim 1, it is characterised in that: the anhydrous polar organic described in step (a) and (b)
Solvent is in dehydrated alcohol, absolute ether or anhydrous propanone one.
Preparation method the most according to claim 1, it is characterised in that: described PVA aqueous solution be polyvinyl alcohol and go from
Sub-water is in mass ratio for the solution of 5-10:100 preparation；The addition of PVA aqueous solution is the 5-15% that forerunner expects powder quality.
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