CN101811828A - NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof - Google Patents

NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof Download PDF

Info

Publication number
CN101811828A
CN101811828A CN200910046465A CN200910046465A CN101811828A CN 101811828 A CN101811828 A CN 101811828A CN 200910046465 A CN200910046465 A CN 200910046465A CN 200910046465 A CN200910046465 A CN 200910046465A CN 101811828 A CN101811828 A CN 101811828A
Authority
CN
China
Prior art keywords
hours
preparation
devitrified glass
solid electrolytes
glass
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.)
Pending
Application number
CN200910046465A
Other languages
Chinese (zh)
Inventor
温兆银
张群喜
宋树丰
吴相伟
黄颖
林久
李宁
王秀艳
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.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
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 Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN200910046465A priority Critical patent/CN101811828A/en
Publication of CN101811828A publication Critical patent/CN101811828A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention relates to NASICON structure glass ceramic sodion solid electrolytes and a preparation method thereof, belonging to the field of solid ionic materials. The NASICON structure glass ceramic solid electrolyte with the chemical formula of Na1+2x+yAxByCzP3O12 is prepared by adopting the traditional ceramic method, wherein A is equal to Mg<2+>, B is equal to Al<3+> or Cr<3+>, C is equal toTi<4+> or Ge<4+>, and the like, x is not less than 0 and is not more than 1, y is not less than 0 and is not more than 1, z is not less than 1 and is not more than 1; and high temperature melting is adopted and is followed by nucleation, crystallization and heat treatment. The invention increases the compactness of the NASICON material, thereby improving the ionic conductivity thereof and expanding the application thereof in the fields of metallurgy, energy, environmental protection, and the like.

Description

NASICON structure devitrified glass sodion solid electrolytes and preparation method thereof
Technical field
The present invention relates to a class and have NASICON structure devitrified glass sodion solid electrolytes and preparation method thereof, belong to solid ionic material field.
Background technology
NASICON (Na Superionic CONductor) is a kind of solid electrolyte material that is worth in numerous areas extensive application such as metallurgy, environmental protection and the energy, is also referred to as the sodium fast-ionic conductor.Early stage sodium fast-ionic conductor is mainly used in sodium-sulfur cell, in recent years, and based on its CO of preparation 2, SO 2, NO xRepresented good application prospects Deng the electrochemistry of solids transmitter, especially CO 2The electrochemistry of solids sensor performance is outstanding.So the preparation of such material and performance become the focus that people pay close attention to.
Known several sodion solid electrolytes has β-Al 2O 3, β "-Al 2O 3, Na 3Zr 2Si 2PO 12(NASICON) etc., all has higher ionic conductivity at a certain temperature.β-Al wherein 2O 3, β "-Al 2O 3Be applied to sodium-sulfur cell, NASICON class material is after them, and another has the solid electrolyte of good ionic conductivity under middle high temperature, and it is applied as the solid electrolyte of gas sensitive device.
The structure of NASICON compound is made up of the open skeleton structure of good three-dimensional octahedra and that tetrahedron forms jointly, Na +Ion transmits in the skeleton gap, because can be along the three-dimensional channel conduction that these gaps constituted, so have higher ionic conductance, its thermal expansion be an isotropy.The method for preparing at present the NASICON material mainly is traditional high-temperature sintering process, but the stupalith pore that this method obtains is more, and compactness is relatively poor, and phase purity is also lower.These shortcomings have limited the application of NASICON material to a certain extent.Seek a kind of method for preparing fine and close NASICON structural compounds, reach and improve its ionic conductivity, and improve the purpose of performances such as its physics, chemistry, mechanics, the NASICON solid electrolyte material is more widely used.The present invention relates to the method that a kind of melt crystallization legal system is equipped with NASICON structure sodion solid electrolytes, do not see similar report at home and abroad as yet.
Summary of the invention
The objective of the invention is to propose a kind of NASICON structure devitrified glass sodion solid electrolytes and preparation method thereof with sodium ion electroconductibility, improve the density of material, and then improve its ionic conductivity, expand its application in fields such as metallurgy, the energy, environmental protection.Concrete steps are as follows:
(1) with carbonate or the acetate of Na, the oxide compound of Mg or carbonate, the oxyhydroxide of Al or oxide compound, the oxide compound of Cr or carbonate, Ga 2O 3, TiO 2, NH 4H 2PO 4Perhaps (NH 4) 2HPO 4And GeO 2According to Na 1+2x+yA xB yC zP 3O 12Stoichiometric ratio batching back ball mill mixing;
Wherein, A=Mg 2+B=Al 3+, Cr 3+Or Ga 3+C=Ti 4+Perhaps Ge 4+Perhaps Ti 4+And Ge 4+0≤x≤1.0,0≤y≤1.0,1≤z≤2.
Wherein preferred C=Ti 4+Or Ge 4+
(2) then in platinum crucible at 1350-1500 ℃ of fusion 1-2 hour, moulding obtained the glass block in 1-2 hour in 450-550 ℃ of annealing (preferred 500 ℃-550 ℃), can be processed into desired shape after the glass cools;
(3) first (570-620 ℃) insulation nucleation at a lower temperature of glass block, soaking time is 1-2 hour, again under comparatively high temps (700-900 ℃) insulation to make crystal growth, heat-up rate in 2-24 hour be 1～5 ℃/minute.Obtain devitrified glass sample of the present invention at last.
Its chemical formula of NASICON structure devitrified glass sodion solid electrolytes that is obtained by aforesaid method is Na 1+2x+yA xB yC zP 3O 12
Wherein, A=Mg 2+B=Al 3+, Cr 3+Or Ga 3+C=Ti 4+Perhaps Ge 4+Perhaps Ti 4+And Ge 4+0≤x≤1.0,0≤y≤1.0,1≤z≤2.
Wherein preferred C=Ti 4+Or Ge 4+
It is gold-plated as blocking electrode that the devitrified glass sample surfaces that obtains is cleaned the back, (described alternating-current impedance spectrometry test is as J.T.S.Irvine to measure its electrochemical properties with AC impedence method, D.C.Sinclair, A.R.West, Adv.Mater.2 (1990) 132-138 is described).The impedance that records by electrochemical impedance spectroscopy can calculate the ionic conductivity of the NASICON microcrystal glass material of the present invention's preparation, and compares with the ionic conductivity of traditional ceramic post sintering method gained material.The result shows, adopts the NASICON solid electrolyte ion specific conductivity of devitrified glass form ceramic high more a lot of than conventional sintering, even two orders of magnitude, and specific conductivity is 1.0 * 10 -5-10 -8About S/c m (150 ℃).
Description of drawings
Fig. 1 is Na 1.4Al 0.4Ge 1.6P 3O 12The XRD figure spectrum of system devitrified glass.Can find out from figure, in this compositional range, the characteristic diffraction peak of sharp-pointed NASICON material appears in material, wherein single diffraction peak correspondence (112) crystal face that exists about 15 °, two diffraction peaks between 20-22 ° respectively corresponding (104), (110) crystal face, the unimodal correspondence about 25 ° Crystal face, unimodal correspondence (024) crystal face about 29 °, the unimodal correspondence about 33 °
Figure B200910046465XD0000022
Crystal face shows that the principal crystalline phase after the mother glass thermal treatment can index change into tripartite NASICON structure;
Fig. 2 is Na 1.8Al 0.8Ti 0.9Ge 0.3P 3O 12The XRD figure spectrum of devitrified glass;
Fig. 3 is Na 1.5Gr 0.5Ge 1.5P 3O 12The XRD figure spectrum of devitrified glass;
Fig. 4 is the Na of preparation 1.4Al 0.4Ge 1.6P 3O 12Devitrified glass section SEM figure; Material microstructure is very fine and close as seen from the figure, does not almost have pore and crackle; The crystal grain eurhythmia, size is about 500nm, and the nanocrystal crystal boundary is clear, and in conjunction with tight, size is even, is irregular polygon or ellipse, and degree of crystallinity is good.
Fig. 5 is Na 1.8Al 0.8Ti 0.9Ge 0.3P 3O 12Devitrified glass section SEM figure;
Fig. 6 is Na 1.5Cr 0.5Ge 1.5P 3O 12Devitrified glass section SEM figure.
Embodiment
Below by concrete comparative example technique effect of the present invention is described, but this non-only be confined to following
Embodiment.
Comparative example 1
Adopt the traditional ceramics sintering process to prepare NASICON type solid electrolyte.With Na 2CO 3, GeO 2, γ-Al 2O 3, (NH 4) H 2PO 4According to Na 1.4Al 0.4Ge 1.6P 3O 12The stoichiometric ratio batching, in mortar, ground 20 minutes, in platinum crucible, be heated to 200 ℃ with 0.1 ℃/minute, and be incubated 4 hours, be heated to 300 ℃ of insulations 8 hours then, the back of pulverizing after the cooling was 725 ℃ of sintering 24 hours, and the back of pulverizing again was 800 ℃ of heating 3 hours, be incubated 70 hours down at 850 ℃ again, obtain precursor powder.Isostatic pressing (150MPa), 725 ℃ of following sintering 24 hours.
Gold calculates the specific conductivity of sample as blocking electrode in the two sides sputter of agglomerating ceramic plate with the AC impedence method measurement.Ionic conductivity under 150 ℃ is 1.1 * 10 -7S/cm.
Comparative example 2
With Na 2CO 3, GeO 2, TiO 2, γ-Al 2O 3, (NH 4) H 2PO 4According to Na 1.8Al 0.8Ti 1.0Ge 0.2P 3O 12The stoichiometric ratio batching, in mortar, ground 20 minutes, in platinum crucible, be heated to 200 ℃ with 0.1 ℃/minute, and be incubated 4 hours, be heated to 300 ℃ of insulations 8 hours then, the back of pulverizing after the cooling was 725 ℃ of sintering 24 hours, and the back of pulverizing again was 800 ℃ of heating 3 hours, be incubated 70 hours down at 850 ℃ again, obtain precursor powder.Isostatic pressing (150MPa), 1000 ℃ of following sintering 3 hours.Gold in the two sides sputter of agglomerating ceramic plate calculates the specific conductivity of sample with the AC impedence method measurement.Ionic conductivity under 150 ℃ is 3.2 * 10 -6S/cm.
Comparative example 3
With Na 2CO 3, GeO 2, Cr 2O 3, (NH 4) H 2PO 4According to Na 1.5Cr 0.5Ge 1.5P 3O 12The stoichiometric ratio batching, in mortar, ground 20 minutes, in platinum crucible, be heated to 200 ℃ with 0.1 ℃/minute, and be incubated 4 hours, be heated to 300 ℃ of insulations 8 hours then, the back of pulverizing after the cooling was 725 ℃ of sintering 24 hours, and the back of pulverizing again was 800 ℃ of heating 3 hours, be incubated 70 hours down at 850 ℃ again, obtain precursor powder.Isostatic pressing (150MPa), 725 ℃ of following sintering 24 hours.
Gold calculates the specific conductivity of sample as blocking electrode in the two sides sputter of agglomerating ceramic plate with the AC impedence method measurement.Ionic conductivity under 150 ℃ is 8.2 * 10 -8S/cm.
Embodiment 1
With Na 2CO 3, Al (OH) 3, NH 4H 2PO 4And GeO 2According to Na 1.4Al 0.4Ge 1.6P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1350 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.The XRD figure spectrum of devitrified glass as shown in Figure 1.Can find out that material has sharp-pointed NASICON characteristic diffraction peak, obtain growing intact NASICON crystalline phase after showing thermal treatment.
Gold is as blocking electrode, with the ionic conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 7.3 * 10 -7S/cm.Relatively example 1, and after visible same material preparation became devitrified glass, ionic conductivity was significantly improved.
Embodiment 2
With Na 2CO 3, Al (OH) 3, NH 4H 2PO 4And GeO 2According to Na 1.6Al 0.6Ge 1.4P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1350 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 800 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the ionic conductivity of AC impedence method specimen in the sputter of devitrified glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 1.2 * 10 -6S/cm.
Embodiment 3
With Na 2CO 3, Al (OH) 3, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ge 1.2P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1400 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 800 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the ionic conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 4.4 * 10 -6S/cm.
Embodiment 4
With Na 2CO 3, Al (OH) 3, NH 4H 2PO 4And GeO 2According to Na 2.0Al 1.0Ge 1.0P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1400 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 800 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the ionic conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 7.3 * 10 -6S/cm.
Embodiment 5
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.2Ge 1.0P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the specific conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 5.4 * 10 -6S/cm.
Embodiment 6
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.4Ge 0.8P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the specific conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 7.5 * 10 -6S/cm.
Embodiment 7
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.6Ge 0.6P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the specific conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 9.6 * 10 -6S/cm.
Embodiment 8
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.8Ge 0.4P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.
Gold is as blocking electrode, with the specific conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 2.3 * 10 -5S/cm.
Embodiment 9
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.9Ge 0.3P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass porcelain sample of the present invention.The XRD figure spectrum of devitrified glass as shown in Figure 2.
Gold is as blocking electrode, with the specific conductivity of AC impedence method specimen in the sputter of microcrystalline glass two sides.Probe temperature is at 150 ℃, and ionic conductivity is 4.4 * 10 -5S/cm.
Embodiment 10
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 1.0Ge 0.2P 30 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 18 hours at last under 620 ℃ and 800 ℃, obtain devitrified glass sample of the present invention.
Gold in the sputter of microcrystalline glass two sides is with the specific conductivity of AC impedence method specimen.Probe temperature is at 150 ℃, and ionic conductivity is 9.4 * 10 -5S/c m.With respect to the traditional ceramics method in the comparative example 2, the glass-ceramic ionic conductivity is greatly improved.
Embodiment 11
With Na 2CO 3, Al (OH) 3, TiO 2, NH 4H 2PO 4And GeO 2According to Na 1.8Al 0.8Ti 0.1Ge 1.1P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 620 ℃ and 750 ℃, obtain devitrified glass sample of the present invention.
Gold in the sputter of microcrystalline glass two sides is with the ionic conductivity of AC impedence method specimen.Probe temperature is at 150 ℃, and ionic conductivity is 7.3 * 10 -5S/cm.
Comparative example 4
With Na 2CO 3, Al (OH) 3, Cr 2O 3, NH 4H 2PO 4And GeO 2According to Na 1.5Cr 0.5Ge 1.5P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 850 ℃, obtain devitrified glass sample of the present invention.The XRD figure spectrum of devitrified glass as shown in Figure 3.
Gold in the sputter of microcrystalline glass two sides is with the ionic conductivity of AC impedence method specimen.Probe temperature is at 150 ℃, and ionic conductivity is 6.2 * 10 -7S/cm.With respect to comparative example 3, the devitrified glass ionic conductivity also is greatly improved.
Comparative example 5
With Na 2CO 3, Al (OH) 3, Cr 2O 3, NH 4H 2PO 4And GeO 2According to Na 1.6Cr 0.6Ge 1.4P 3O 12The stoichiometric ratio batching, ball mill mixing is 4 hours in the alcohol medium, oven dry, 300 ℃ and 600 ℃ are incubated 2 hours respectively and 4 hours, fusion cast glass under 1450 ℃ of high temperature, moulding, annealing, the cooling post-treatment is incubated 2 hours respectively and 12 hours at last under 600 ℃ and 850 ℃, obtain devitrified glass sample of the present invention.
Gold in the sputter of microcrystalline glass two sides is with the ionic conductivity of AC impedence method specimen.Probe temperature is at 150 ℃, and ionic conductivity is 5.6 * 10 -7S/cm.
As seen from the above-described embodiment, the present invention has had following advantage: the density of material is increased, and the material of densification has lower resistance and stronger solid ionic transmittability; 2. specific conductivity is significantly improved, and the densification of material helps Na +Transmission; 3. preparation method's technology of the present invention is simple, utilizes the advantage of glass preparation, can be prepared into the sample of any required shape.

Claims (8)

1.NASICON structure devitrified glass sodion solid electrolytes is characterized in that chemical formula is Na 1+2x+yA xB yC zP 3O 12
Wherein, A=Mg 2+B=Al 3+, Cr 3+Or Ga 3+C=Ti 4+Perhaps Ge 4+Perhaps Ti 4+And Ge 4+0≤x≤1.0,0≤y≤1.0,1≤z≤2.
2. by the described NASICON structure of claim 1 devitrified glass sodion solid electrolytes, it is characterized in that C=Ti 4+Or Ge 4+
3.NASICON the preparation method of structure devitrified glass sodion solid electrolytes is characterized in that, comprises the steps:
(1) with carbonate or the acetate of Na, the oxide compound of Mg or carbonate, the oxyhydroxide of Al or oxide compound, the oxide compound of Cr or carbonate, Ga 2O 3, TiO 2, NH 4H 2PO 4Perhaps (NH 4) 2HPO 4And GeO 2According to Na 1+2x+yA xB yC zP 3O 12Stoichiometric ratio batching back ball mill mixing;
Wherein, A=Mg 2+B=Al 3+, Cr 3+Or Ga 3+C=Ti 4+Perhaps Ge 4+Perhaps Ti 4+And Ge 4+0≤x≤1.0,0≤y≤1.0,1≤z≤2;
(2) then at 1350-1500 ℃ of fusion 1-2 hour, moulding obtained the glass block in 1-2 hour 450-550 ℃ of annealing;
(3) the glass block is incubated nucleation at a lower temperature, is incubated under comparatively high temps again.
4. by the preparation method of the described NASICON structure of claim 3 devitrified glass sodion solid electrolytes, it is characterized in that described C=Ti 4+Or Ge 4+
5. by the preparation method of claim 3 or 4 described NASICON structure devitrified glass sodion solid electrolytes, it is characterized in that described annealing temperature is 500 ℃-550 ℃.
6. by the preparation method of claim 3 or 4 described NASICON structure devitrified glass sodion solid electrolytes, it is characterized in that lesser temps is 570-620 ℃ of insulation in the described step (3), soaking time is 1-2 hour.
7. by the preparation method of claim 3 or 4 described NASICON structure devitrified glass sodion solid electrolytes, it is characterized in that comparatively high temps is 700-900 ℃ of insulation in the described step (3), soaking time is 2-24 hour.
8. by the preparation method of claim 3 or 4 described NASICON structure devitrified glass sodion solid electrolytes, it is characterized in that the fusion environment is a platinum crucible in the described step (2).
CN200910046465A 2009-02-23 2009-02-23 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof Pending CN101811828A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910046465A CN101811828A (en) 2009-02-23 2009-02-23 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910046465A CN101811828A (en) 2009-02-23 2009-02-23 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof

Publications (1)

Publication Number Publication Date
CN101811828A true CN101811828A (en) 2010-08-25

Family

ID=42619220

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910046465A Pending CN101811828A (en) 2009-02-23 2009-02-23 NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101811828A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104600355A (en) * 2015-01-07 2015-05-06 南京邮电大学 All-solid-state sodium ion electrolyte containing micro nanocrystal and preparation method thereof
CN104900912A (en) * 2015-05-28 2015-09-09 燕山大学 Na fast-ion conductor Na3PSe4 and preparation method thereof
CN105609871A (en) * 2016-01-22 2016-05-25 昆明理工大学 Preparation method of sodium-ion solid electrolyte with NASICON structure
CN105655630A (en) * 2016-02-05 2016-06-08 中国科学院西安光学精密机械研究所 NASICON type magnesium ion solid electrolyte and preparation method thereof
CN106663550A (en) * 2014-02-26 2017-05-10 波尔图大学 A solid electrolyte glass for lithium or sodium ions conduction
US10173921B2 (en) 2013-08-28 2019-01-08 Corning Incorporated Lithium orthophosphate glasses, corresponding glass-ceramics and lithium ion-conducting NZP glass ceramics
US10361454B2 (en) 2016-07-11 2019-07-23 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
CN110078041A (en) * 2019-04-26 2019-08-02 北京金羽新能科技有限公司 A kind of sodium ion superconductor Na1+xAlxTi2-x(PO4)3And its preparation method and application
CN110212240A (en) * 2019-06-26 2019-09-06 上海空间电源研究所 Lithium ion solid electrolyte and preparation method thereof
US10490360B2 (en) 2017-10-12 2019-11-26 Board Of Regents, The University Of Texas System Heat energy-powered electrochemical cells
CN111261935A (en) * 2020-03-04 2020-06-09 四川固蜀材料科技有限公司 Sodium ion conductor solid electrolyte material, preparation method and application

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10173921B2 (en) 2013-08-28 2019-01-08 Corning Incorporated Lithium orthophosphate glasses, corresponding glass-ceramics and lithium ion-conducting NZP glass ceramics
US10411293B2 (en) 2014-02-26 2019-09-10 Universidade Do Porto Solid electrolyte glass for lithium or sodium ions conduction
CN106663550A (en) * 2014-02-26 2017-05-10 波尔图大学 A solid electrolyte glass for lithium or sodium ions conduction
CN106663550B (en) * 2014-02-26 2019-03-01 波尔图大学 For lithium or the solid electrolyte glass of sodium ion conduction
CN104600355B (en) * 2015-01-07 2016-09-14 南京邮电大学 A kind of all-solid sodium ion electrolyte containing micro nanocrystalline and preparation method thereof
CN104600355A (en) * 2015-01-07 2015-05-06 南京邮电大学 All-solid-state sodium ion electrolyte containing micro nanocrystal and preparation method thereof
CN104900912A (en) * 2015-05-28 2015-09-09 燕山大学 Na fast-ion conductor Na3PSe4 and preparation method thereof
CN105609871A (en) * 2016-01-22 2016-05-25 昆明理工大学 Preparation method of sodium-ion solid electrolyte with NASICON structure
CN105655630A (en) * 2016-02-05 2016-06-08 中国科学院西安光学精密机械研究所 NASICON type magnesium ion solid electrolyte and preparation method thereof
US10361454B2 (en) 2016-07-11 2019-07-23 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
US10511055B2 (en) 2016-07-11 2019-12-17 Board Of Regents, The University Of Texas System Metal plating-based electrical energy storage cell
US10490360B2 (en) 2017-10-12 2019-11-26 Board Of Regents, The University Of Texas System Heat energy-powered electrochemical cells
US10804040B2 (en) 2017-10-12 2020-10-13 Hydro-Quebec Heat energy-powered electrochemical cells
US11049667B2 (en) 2017-10-12 2021-06-29 Hydro-Quebec Heat energy-powered electrochemical cells
CN110078041A (en) * 2019-04-26 2019-08-02 北京金羽新能科技有限公司 A kind of sodium ion superconductor Na1+xAlxTi2-x(PO4)3And its preparation method and application
CN110212240A (en) * 2019-06-26 2019-09-06 上海空间电源研究所 Lithium ion solid electrolyte and preparation method thereof
CN111261935A (en) * 2020-03-04 2020-06-09 四川固蜀材料科技有限公司 Sodium ion conductor solid electrolyte material, preparation method and application

Similar Documents

Publication Publication Date Title
CN101811828A (en) NASICON structure glass ceramic sodion solid electrolytes and preparation method thereof
Hallopeau et al. Microwave-assisted reactive sintering and lithium ion conductivity of Li1. 3Al0. 3Ti1. 7 (PO4) 3 solid electrolyte
Leo et al. Lithium conducting glass ceramic with Nasicon structure
Anantharamulu et al. A wide-ranging review on Nasicon type materials
Zhuang et al. Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics
Duluard et al. Lithium conducting solid electrolyte Li1. 3Al0. 3Ti1. 7 (PO4) 3 obtained via solution chemistry
Zhu et al. Influence of crystallization temperature on ionic conductivity of lithium aluminum germanium phosphate glass-ceramic
EP3244474B1 (en) Oriented apatite-type oxide ion conductor and method for manufacturing same
CN104628381A (en) Method for preparing aluminum substituted garnet
EP2181971A1 (en) Glass and glass-ceramics
JP2010030840A (en) Method of manufacturing lithium ion conductive glass ceramic
CN109626996A (en) A kind of ferro-aluminum codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof
JP3012211B2 (en) Lithium ion conductive glass ceramics and batteries and gas sensors using the same
CN104659412A (en) Lithium-carbon-boron oxide solid electrolyte material containing plane triangle group and battery
CN104557058A (en) Method for preparing high-transparency transparent electrooptic ceramics by performing composite vacuum-oxygen hot pressed sintering
INAGUMA et al. Lithium ion conductivity in a perovskite lanthanum lithium titanate single crystal
KR101982422B1 (en) Lithium ion conductive crystal body and all-solid state lithium ion secondary battery
Garai et al. Zr+ 4-controlled nucleation and microstructure in Si-Mg-Al-KBF glass-ceramic sealant (solid oxide fuel cell)
Liu et al. Synthesis of Li7La3Zr2O12 solid electrolyte by solid phase sintering method
Zhao et al. Dense garnet-like Li5La3Nb2O12 solid electrolyte prepared by self-consolidation method
WO2013180658A1 (en) Glass ceramic electrolyte system
Kawada et al. Synthesis and characterization of Na+ conducting glass-ceramic Na5FeSi4O12 doped with boron, aluminum, and gallium oxides
Raj et al. Electrical conductivity, oxygen diffusion and surface exchange studies on a melilite-type La1. 05Sr0. 95Ga3O7+ δ
CN101811829B (en) Preparation method of chalcogenide microcrystalline glass material with function of lithium ion conductor
Yan et al. Enhancing the ionic conductivity and stabilizing cubic structure of garnet-type Li6. 25-xAl0. 25La3Zr2-xTaxO12 by Al/Ta co-doping

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20100825