CN103466588A - Preparation method of NASICON type lithium fast ion conductor - Google Patents
Preparation method of NASICON type lithium fast ion conductor Download PDFInfo
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Abstract
The invention discloses a preparation method of an NASICON type lithium fast ion conductor. The preparation method comprises the following steps: adding butyl titanate into a citric acid solution, uniformly stirring the solution, adding a citric acid solution of lithium nitrate, aluminum nitrate and diammonium phosphate, uniformly stirring the solution and adding ethylene glycol, heating the solution to a certain temperature, and stirring the solution to completely gelatinize the same; drying the gel to obtain dry gel, and grinding and calcining the dry gel to obtain precursor powder; and grinding the precursor powder fine powder, carrying out isostatic press molding on the fine powder on a tablet press to obtain an electrolyte sheet of the NASICON type lithium fast ion conductor. The preparation method is used for reducing the sintering temperature of the material, perfecting the sintering performance of the material and improving the density of the material to improve the ionic conductivity of the material. The ionic conductivity of the NASICON type lithium fast ion conductor prepared by the preparation method reaches 6.34*10<-4> S/cm (25 DEG C), so that compared with a traditional preparation method, the ionic conductivity is significantly improved.
Description
Technical field
The invention belongs to the preparation field of lithium fast-ionic conductor, particularly relate to a kind of preparation method of NASICON type lithium fast-ionic conductor.
Background technology
Energy problem and environmental problem become two large bottlenecks of restriction human social development.By inference, to the year two thousand fifty, the mankind will be present twices to the demand of electric energy.For reducing the dependence to oil, the renewable energy sources such as sun power, wind energy, tidal energy are extensively paid attention to, are studied and utilized, and in the process of effectively utilizing these energy, storage and the transmission problem of energy are needed solution badly.Researching and developing efficient, safe, green chemical power source is the effective way addressed this problem.
Solid electrolyte is the critical material of high-performance energy storage device of future generation, is effective substitute of liquid organic electrolyte in the high-energy-density chemical cell device.Three-D space structure NASICON type lithium fast-ionic conductor is as a kind of solid electrolyte, than the lithium fast-ionic conductor of other types as sulfide system, polymeric system, Li
3n etc., because of the easily preparation of its safety, high ionic conductivity, wide electrochemical window, excellent chemistry and electrochemical stability, the advantage such as easily assembling and preparation cost be low and by people's extensive concern.
The structure of NASICON type compound is by MO
6octahedron and AO
4interconnection and the Three-dimensional Open skeleton structure that forms of tetrahedron drift angle, Li
+in the formed passage in gap in the Three-dimensional Open skeleton structure, conducted, transport number is 1, therefore have higher ionic conductivity.The method for preparing at present NASICON type structural compounds is mainly traditional high temperature solid-state method, melting method of cooling etc., although the preparation technology of this method is simple, energy consumption is high, and resulting stupalith phase purity is low, and specific conductivity is low, and pore is many, and compactness is poor.These shortcomings have limited the application of NASICON shaped material on certain degree.Therefore, explore a kind of simple method for preparing high conductivity NASICON type lithium fast-ionic conductor of design, seem and be necessary very much.
Summary of the invention
For the existing the problems referred to above of prior art and demand, the preparation method who the purpose of this invention is to provide a kind of NASICON type lithium fast-ionic conductor, to reduce the material grains size, improve the coking property of material, improve the density of material, and then improve its ionic conductivity, expand the application of this material in the high-performance energy storage device.
The present invention solves the problems of the technologies described above adopted technical scheme:
A kind of preparation method of NASICON type lithium fast-ionic conductor, the chemical general formula of described NASICON type lithium fast-ionic conductor is Li
1+xal
xti
2～x(PO
4)
3, 0.1≤x≤0.5; It can be at room temperature be greater than 10 to air and moisture stabilization and lithium ion conductivity
～4s/cm;
Described preparation method comprises the following steps:
(1) under the isoperibol of 80～90 ℃, tetrabutyl titanate is dissolved in citric acid solution, after stirring 20h～25h, form colloidal sol; Wherein, the concentration of described citric acid solution is 0.2～0.3mol/L, and in described colloidal sol, citric acid is 1:1 with the ratio of the amount of substance of metallic cation;
(2) by lithium nitrate, aluminum nitrate and primary ammonium phosphate mix; Wherein, described in lithium nitrate, aluminum nitrate, primary ammonium phosphate and step (1), the stoichiometric ratio of tetrabutyl titanate is (1+x): x:3:(2～x);
Mixture after batching is dissolved in citric acid solution, stirs and make it become the nitrate mixed solution of transparent homogeneous; Wherein, the concentration of described citric acid solution is 0.2～0.3mol/L, and in described nitrate mixed solution, citric acid is 1:1 with the ratio of the amount of substance of metallic cation; Citric acid solution in this step is identical with the citric acid solution in step (1);
(3) under the isoperibol of 80～90 ℃, the nitrate mixed solution of preparation in step (2) is joined in the prepared colloidal sol of step (1) slowly, stir 0.5h～1h;
Add afterwards with current mixed solution in the equimolar ethylene glycol of citric acid amount, thermostat temperature is adjusted to 100 ℃～130 ℃, heat 5～10h, make the mixed solution polyesterification reaction complete, generate block gel;
(4) the resulting block gel of step (3) is placed in to heat treatment furnace, Heating temperature is 150～200 ℃, and be 6h～8h heat-up time, makes block gel become xerogel; Take out xerogel, and xerogel is ground into to powder granule;
(5) powder granule of preparation in step (4) being put into to heat treatment furnace again, is under 400～500 ℃ in temperature, is incubated 4～6h; Then temperature rises to 800～830 ℃, is incubated 1～2h, takes out afterwards particulate matter; This particulate matter is ground to form to fine powder, obtain precursor;
(6), under the pressing machine that is 200～500Mpa by the precursor of preparation in step (5) at pressure, pressurize 10～20min, be pressed into base substrate;
(7) base substrate of preparation in step (6) is put into to heat treatment furnace, adjust the temperature to 850～1000 ℃, thermal treatment 6～10h, sintering obtains NASICON type lithium fast-ionic conductor electrolyte sheet.
The further setting of the present invention is, the material in step (4), step (5) and step (7) in heat treatment furnace, with the temperature rise rate of 2～5 ℃/per minute to corresponding thermal treatment temp.
The further setting of the present invention is, described isoperibol refers to the oil bath environment.The process that forms theoretically colloidal sol is used water-bath also passable, but, due to whipping temp high (80～90 ℃), churning time is long, and the water capacity in water-bath easily evaporates, and uses the words of water-bath to need the continual water that adds, pretty troublesome, therefore preferably use oil bath.
The preparation method of NASICON type lithium fast-ionic conductor of the present invention (abbreviation sol-gel method) mainly comprises the calcination process of configuration, plastic, drying and the xerogel of initial colloidal sol.The present invention has overcome high temperature solid-state method energy consumption height and the low shortcoming of prepared phase purity, the present invention adopts sol-gel method, can realize preparing the presoma starting material and reach other mixing of molecular level, other is blended in the easy while that element doping is become this molecular level, also reduced the sintering temperature of material, improve the sintering character of material, improved the density of material to improve its ionic conductivity, expanded the application of this material in the high-performance energy storage device.
After with 800 purpose aluminum oxide sandpapers, resulting lithium fast-ionic conductor thin slice two sides being polished smooth, two-sided gold-plated as blocking electrode, measure its electrochemical properties by two electrode AC impedance methods.Test out electrochemical impedance spectroscopy by electrochemical impedance, by impedance spectrum, measured impedance can be calculated the ionic conductivity of NASICON type lithium fast-ionic conductor material prepared by the present invention.Result shows, the ionic conductivity of the NASICON type lithium fast-ionic conductor that adopts preparation method of the present invention to prepare has reached 6.34 * 10
～4s/cm (25 ℃), compare with traditional preparation method, and ionic conductivity significantly improves.
The accompanying drawing explanation
Fig. 1 is the prepared Li of high temperature solid-state method
1.4al
0.4ti
1.6(PO
4)
3the XRD figure spectrum of powder;
Fig. 2 is 900 ℃ of prepared resulting Li of lower sintering 6h of sol-gel method
1.4al
0.4ti
1.6(PO
4)
3the XRD figure of lamellar body;
Fig. 3 is Li
1.4al
0.4ti
1.6(PO
4)
3the SEM figure of powder;
Fig. 4 is 900 ℃ of resulting Li of lower sintering 6h
1.4al
0.4ti
1.6(PO
4)
3the FSEM figure of sheet body section;
Fig. 5 is 900 ℃ of resulting Li of lower sintering 6h
1.4al
0.4ti
1.6(PO
4)
3the EIS figure of lamellar body;
The EIS figure of the LATP lamellar body that Fig. 6 is sintering 6h under different sintering temperatures.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, for the explanation of these embodiments, for helping to understand the present invention, but do not form limitation of the invention.In addition, below in each embodiment of described the present invention involved technical characterictic as long as form each other conflict, just can mutually not combine.
Comparative example 1
The method that adopts the conventional high-temperature solid phase method to prepare NASICON type lithium fast-ionic conductor is: by Quilonum Retard, aluminum nitrate, titanium dioxide, primary ammonium phosphate according to Li
1.4al
0.4ti
1.6(PO
4)
3stoichiometric ratio batching is ground 1h in agate mortar, in corundum crucible, with 2 ℃/min, is heated to 500 °, and insulation 4h, after pulverizing after cooling, in corundum crucible, with 2 ℃/min, is heated to 1450 ℃ and be incubated 2h.Cooling rear taking-up is also pulverized, and obtains precursor powder.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 1.02 * 10
～4s/cm (25 ℃).Fig. 1 is the prepared Li of high temperature solid-state method
1.4al
0.4ti
1.6(PO
4)
3the XRD figure spectrum of powder.As can be seen from the figure, in this compositional range, sharp-pointed NASICON material characteristics diffraction peak appears in material.
Embodiment 1
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.1al
0.1ti
1.9(PO
4)
3(x=0.1) batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule (in the present invention, powder granule does not have big or small requirement, as long as be particulate state) in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor (the present invention does not have big or small requirement to precursor, so long as little fine powder gets final product than powder granule size).Isostatic pressing (200Mpa) afterwards, pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 9.25 * 10
～5s/cm (25 ℃).
Embodiment 2
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.2al
0.2ti
1.8(PO
4)
3(x=0.2) batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, adjusts the temperature to 500 ℃, 2 ℃/min of temperature rise rate, insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 1.13 * 10
～4s/cm (25 ℃).
Embodiment 3
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.3al
0.3ti
1.7(PO
4)
3(x=0.3) batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 3.68 * 10
～4s/cm (25 ℃).
Embodiment 4
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3(x=0.4) batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
Fig. 2 is 900 ℃ of prepared resulting Li of lower sintering 6h of sol-gel method
1.4al
0.4ti
1.6(PO
4)
3the XRD figure of lamellar body; As can be seen from the figure, sharp-pointed LiTi appears in material
2(PO
4)
3characteristic diffraction peak, and dephasign AlPO do not detected
4existence, show that we prepare the powder than pure phase by this method.
Fig. 3 is prepared Li
1.4al
0.4ti
1.6(PO
4)
3the SEM figure of powder, diameter of particle is evenly distributed as seen from the figure, probably in the 300nm left and right.
Fig. 4 is prepared Li
1.4al
0.4ti
1.6(PO
4)
3the FSEM figure of sheet body section, as can be seen from the figure, homogeneous grain size, degree of crystallinity is good, is irregular polygon, and crystal grain contacts with intergranule closely, and the crystal boundary face is unintelligible, almost there is no pore and crackle, and material microstructure is very fine and close;
Fig. 5 is prepared Li
1.4al
0.4ti
1.6(PO
4)
3the EIS figure of lamellar body; Can obtain grain resistance and grain boundary resistance from figure, be 6.34 * 10 through the specific conductivity that can be calculated lithium fast-ionic conductor
～4s/cm (25 ℃).
Embodiment 5
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.5al
0.5ti
1.5(PO
4)
3(x=0.5) batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, with the AC impedence method measurement, calculates to such an extent that its ionic conductivity is 3.32 * 10
～4s/cm (25 ℃).
Embodiment 6
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 850 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and its ionic conductivity calculated with the AC impedence method measurement is 2.11 * 10
～4s/cm (25 ℃).
Embodiment 7
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 950 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 3.21 * 10
～4s/cm (25 ℃).
Embodiment 8
Regulating oil bath temperature is 90 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 1000 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 2.18 * 10
～4s/cm (25 ℃).
Embodiment 9
Regulating oil bath temperature is 80 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 300ml, in the 0.2mol/L citric acid solution, after stirring 20h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 250ml, in the 0.2mol/L citric acid solution after, slowly add in colloidal sol, after stirring 0.5h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 120 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 150 ℃, and insulation 8h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 2 ℃/min of temperature rise rate, adjust the temperature to 500 ℃, and insulation 4h, then be warmed up to 800 ℃, insulation 2h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (200Mpa), pressurize 20min, 900 ℃ of lower sintering 6h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 5.36 * 10
～4s/cm (25 ℃).
Regulating oil bath temperature is 85 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 200ml, in the 0.3mol/L citric acid solution, after stirring 25h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 167ml, in the 0.3mol/L citric acid solution after, slowly add in colloidal sol, after stirring 1h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 130 ℃, after heating 5h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 200 ℃, and insulation 6h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 5 ℃/min of temperature rise rate, adjust the temperature to 400 ℃, and insulation 6h, then be warmed up to 830 ℃, insulation 1h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (500Mpa), pressurize 10min, 900 ℃ of lower sintering 10h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 2.06 * 10
～4s/cm (25 ℃).
Embodiment 11
Regulating oil bath temperature is 85 ℃, and the 17.6ml tetrabutyl titanate is dissolved in to 200ml, in the 0.3mol/L citric acid solution, after stirring 25h, forms colloidal sol.By lithium nitrate, aluminum nitrate, primary ammonium phosphate according to stoichiometric ratio Li
1.4al
0.4ti
1.6(PO
4)
3batching, be dissolved in 167ml, in the 0.3mol/L citric acid solution after, slowly add in colloidal sol, after stirring 1h, add 6.12ml ethylene glycol, oil bath temperature is adjusted to 100 ℃, after heating 10h, take out, form gel.Gel, as in the corundum crucible in retort furnace, is adjusted the temperature to 200 ℃, and insulation 6h, make it become xerogel.By xerogel as for grinding into powder granule in agate mortar.This powder granule is placed in again to the crucible of retort furnace, 5 ℃/min of temperature rise rate, adjust the temperature to 400 ℃, and insulation 6h, then be warmed up to 820 ℃, insulation 1.5h.Cooling rear taking-up is placed in agate mortar and grinds 1h, obtains precursor.Isostatic pressing (500Mpa), pressurize 10min, 900 ℃ of lower sintering 10h.
The ceramic plate two sides splash gold electrode of sintering is done blocking electrode, and calculating its ionic conductivity with the AC impedence method measurement is 2.24 * 10
～4s/cm (25 ℃).
The EIS figure of the LATP lamellar body that Fig. 6 is sintering 6h under different sintering temperatures, as can be seen from the figure, 900 ℃ of prepared lamellar bodies of lower sintering 6h have the highest specific conductivity.
Performance and preparation process by contrast sol-gel method (embodiment 1～11) and the prepared material of high temperature solid-state method (comparative example 1), can draw, the diameter of particle prepared by sol-gel method is even, and phase purity is high, energy consumption is low, and the ionic conductivity of material is higher.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.Do not break away from the equivalence completed under spirit disclosed in this invention so every or revise, all falling into the scope of protection of the invention.
Claims (3)
1. the preparation method of a NASICON type lithium fast-ionic conductor, the chemical general formula of described NASICON type lithium fast-ionic conductor is Li
1+xal
xti
2～x(PO
4)
3, 0.1≤x≤0.5; It is characterized in that, described preparation method comprises the following steps:
(1) under the isoperibol of 80～90 ℃, tetrabutyl titanate is dissolved in citric acid solution, after stirring 20h～25h, form colloidal sol; Wherein, the concentration of described citric acid solution is 0.2～0.3mol/L, and in described colloidal sol, citric acid is 1:1 with the ratio of the amount of substance of metallic cation;
(2) by lithium nitrate, aluminum nitrate and primary ammonium phosphate mix; Wherein, described in lithium nitrate, aluminum nitrate, primary ammonium phosphate and step (1), the stoichiometric ratio of tetrabutyl titanate is (1+x): x:3:(2～x):
Mixture after batching is dissolved in citric acid solution, stirs and make it become the nitrate mixed solution of transparent homogeneous; Wherein, the concentration of described citric acid solution is 0.2～0.3mol/L, and in described nitrate mixed solution, citric acid is 1:1 with the ratio of the amount of substance of metallic cation;
(3) under the isoperibol of 80～90 ℃, the nitrate mixed solution of preparation in step (2) is joined in the prepared colloidal sol of step (1) slowly, stir 0.5h～1h;
Add afterwards with current mixed solution in the equimolar ethylene glycol of citric acid amount, thermostat temperature is adjusted to 100 ℃～130 ℃, heat 5～10h, make the mixed solution polyesterification reaction complete, generate block gel;
(4) the resulting block gel of step (3) is placed in to heat treatment furnace, Heating temperature is 150～200 ℃, and be 6h～8h heat-up time, makes block gel become xerogel; Take out xerogel, and xerogel is ground into to powder granule;
(5) powder granule of preparation in step (4) being put into to heat treatment furnace again, is under 400～500 ℃ in temperature, is incubated 4～6h; Then temperature rises to 800～830 ℃, is incubated 1～2h, takes out afterwards particulate matter; This particulate matter is ground to form to fine powder, obtain precursor;
(6), under the pressing machine that is 200～500Mpa by the precursor of preparation in step (5) at pressure, pressurize 10～20min, be pressed into base substrate;
(7) base substrate of preparation in step (6) is put into to heat treatment furnace, adjust the temperature to 850～1000 ℃, thermal treatment 6～10h, sintering obtains NASICON type lithium fast-ionic conductor electrolyte sheet.
2. the preparation method of NASICON type lithium fast-ionic conductor according to claim 1, it is characterized in that, material in step (4), step (5) and step (7) in heat treatment furnace, with the temperature rise rate of 2～5 ℃/per minute to corresponding thermal treatment temp.
3. the preparation method of NASICON type lithium fast-ionic conductor according to claim 1, is characterized in that, described isoperibol refers to the oil bath environment.
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