CN102709578A - Indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material and preparation method thereof - Google Patents
Indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material and preparation method thereof Download PDFInfo
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- CN102709578A CN102709578A CN2012101827968A CN201210182796A CN102709578A CN 102709578 A CN102709578 A CN 102709578A CN 2012101827968 A CN2012101827968 A CN 2012101827968A CN 201210182796 A CN201210182796 A CN 201210182796A CN 102709578 A CN102709578 A CN 102709578A
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Abstract
The invention discloses an indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material and a preparation method thereof, which relate to a solid electrolyte material and the preparation method thereof and aim at solving the problems of high cost of a sol-gel method for preparing an epoxide apatite type lanthanum silicate mixed solid electrolyte material and high temperature, high energy consumption and easiness in forming a second phase of a high-temperature solid phase reaction method for preparing the epoxide apatite type lanthanum silicate mixed solid electrolyte material. The chemical formula of the electrolyte material is La10Si(6-x)InxO(27-x/2) or La10Si(6-x)NbxO(27+x/2), the preparation method of the electrolyte material comprises the following steps of: pre-sintering in low temperature after La2O3, SiO2 and In2O3 (or Nb2O5) are mixed in wet way, dried and screened, carrying out cold press molding, then carrying out cold isostatic pressing, and obtaining a product by pressureless-sintering finally. The indium or niobium epoxide apatite type lanthanum silicate mixed solid electrolyte material disclosed by the invention has the advantages that the cost is low, the period is short, the energy consumption is low, the product has higher electric conductivity under middle and low temperature, and the service life of a solid-oxide fuel cell can be facilitated to be increased. The electrolyte material disclosed by the invention is used for the solid-oxide fuel cell.
Description
Technical field
The present invention relates to solid electrolyte material and preparation method thereof.
Background technology
Fuel cell is a kind of efficient, eco-friendly electrochemical energy conversion equipment, becomes the most potential green energy resource of 21 century with its unique advantage.Wherein (Solid Oxide Fuel Cells SOFCs) owing to have advantages such as high energy conversion efficiency, simple in structure, no liquid corrosion and losing issue and life-span be long, has caused people's extensive concern to SOFC.The zirconia (YSZ) that mainly uses stabilized with yttrium oxide in the commercial applications at present is as electrolyte, but this material require just can be kept its high ionic conductivity under the high temperature of 1273K, because serviceability temperature is too high; Cause electrolyte aging; Electrode be connected material and select difficulty, start-up time is long, the manufacturing cost height; Problems such as sealing and structural problem and long-time run stability, therefore higher operating temperature has limited development and the use of SOFCs to a certain extent.
Oxygen base apatite-type lanthanum silicate electrolyte has high ionic conductivity and low activation energy under middle low temperature; And its thermal coefficient of expansion and anode and cathode material are complementary; A kind of novel electrolytes material of excellent performance be might become, thereby middle low temperature process and the commercialized development of SOFCs quickened.The preparation method of present this electrolyte mainly is high-temperature solid phase reaction method and sol-gal process.The diameter of particle of Prepared by Sol Gel Method is little and even, and sintering temperature is lower, but the pure salt cost of employed metal is higher; High-temperature solid phase reaction method is simple to operate; Cost is low; Be the most frequently used so far preparation method; But the employed oxide powder of high-temperature solid phase reaction method need be incubated the lanthanum silicate phase that 10～30h could synthesize oxygen base apatite structure being higher than under the temperature of 1873K, and because that powder mixes is inhomogeneous, normal formation hinders the second phase La that conductivity improves
2SiO
5Or La
2Si
2O
7, the existence of second phase has also influenced the carrying out of solid phase reaction densification, is unfavorable for the raising of conductivity.
Summary of the invention
The present invention will solve the sol-gal process cost height of existing preparation oxygen base apatite-type lanthanum silicate electrolyte and the high-temperature solid phase reaction method temperature is high, energy consumption is big, be prone to form the problem of second phase, and a kind of indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material and preparation method thereof are provided.
The chemical formula of indium of the present invention or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is La
10Si
6-xIn
xO
27-x/2Or La
10Si
6-xNb
xO
27+x/2, wherein, the span of x is 0＜x≤2.
The preparation method of above-mentioned indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3, SiO
2Place three crucibles respectively with A, again crucible is placed high temperature furnace, with 100～300Kh
-1Programming rate be warming up to 873～1273K, the insulation 1～4h after, with 100～500Kh
-1Cooling rate reduce to room temperature; Wherein A represents In
2O
3Or Nb
2O
5
Two, take by weighing the La that handles through step 1
2O
3, SiO
2And A, wherein La
2O
3With SiO
2The ratio of amount of substance be 5: (5.5～5.9), La
2O
3With the ratio of the amount of substance of A be 5: (0.05～0.25);
Three, with the La that takes by weighing in the step 2
2O
3, SiO
2Place ball grinder with A, add absolute ethyl alcohol and abrading-ball, wet-milling mixes, and obtains mixture; Wherein the mass ratio of powder and absolute ethyl alcohol is 1: (0.5～3), the mass ratio of powder and abrading-ball are 1: (3～5); The quality of powder is meant La
2O
3, SiO
2Gross mass with A;
Four, behind the mixture oven dry that step 3 is obtained, mistake 160～500 mesh sieves, the temperature lower calcination 5～15h at 1473～1673K obtains calcining powder;
Five, the calcining powder cold moudling under the pressure of 10～40MPa that step 4 is obtained, cold isostatic compaction under 100～400MPa again, the dwell time is 3～10min, obtains base substrate;
Six, be under the condition of 1773～1973K in temperature with the base substrate that obtains in the step 5, sintering 5～30h obtains indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
The invention has the beneficial effects as follows:
1, compare with sol-gal process, cost of material used in the present invention is low, and preparation technology is simple, and the cycle is short;
2, doping oxide has reduced required sintering temperature of high-temperature solid phase reaction method and temperature retention time, thereby has reduced energy consumption;
3, doping oxide has reduced by second phase content, has improved the density of oxygen base apatite-type lanthanum silicate solid electrolyte material;
4, compare with doped with oxygen base apatite-type lanthanum silicate solid electrolyte not; (873～1073K) conductivity is doubled many, helps improving the useful life of SOFC under middle low temperature for indium that the present invention synthesized or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte.
Electrolyte of the present invention is used for SOFC.
Description of drawings
Fig. 1 is the unadulterated La that contrast test one is synthesized
10Si
6O
27XRD spectra, peak position shown in " ο " is the second phase La
2SiO
5Characteristic peak;
Fig. 2 is embodiment one products therefrom La
10Si
5.5In
0.5O
26.75XRD spectra;
Fig. 3 is embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25XRD spectra;
Fig. 4 is embodiment one products therefrom La
10Si
5.5In
0.5O
26.75The AC impedance spectrogram;
Fig. 5 is embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25The AC impedance spectrogram;
Fig. 6 is a total conductivity Arrhenius curve, and wherein " ο " represents embodiment one products therefrom La
10Si
5.5In
0.5O
26.75Total conductivity Arrhenius curve,
Represent embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25Total conductivity Arrhenius curve, " " represents the synthetic unadulterated La of contrast test one
10Si
6O
27Total conductivity Arrhenius curve.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the chemical formula of this execution mode indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is La
10Si
6-xIn
xO
27-x/2Or La
10Si
6-xNb
xO
27+x/2, wherein, the span of x is 0＜x≤2.
The beneficial effect of this execution mode is:
1, doping oxide has reduced by second phase content, has improved the density of oxygen base apatite-type lanthanum silicate solid electrolyte material;
2, compare with doped with oxygen base apatite-type lanthanum silicate solid electrolyte not; (873～1073K) conductivity is doubled many, helps improving the useful life of SOFC under middle low temperature for indium that the present invention synthesized or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte.
Embodiment two: the preparation method of this execution mode indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3, SiO
2Place three crucibles respectively with A, again crucible is placed high temperature furnace, with 100～300Kh
-1Programming rate be warming up to 873～1273K, the insulation 1～4h after, with 100～500Kh
-1Cooling rate reduce to room temperature; Wherein A represents In
2O
3Or Nb
2O
5
Two, take by weighing the La that handles through step 1
2O
3, SiO
2And A, wherein La
2O
3With SiO
2The ratio of amount of substance be 5: (5.5～5.9), La
2O
3With the ratio of the amount of substance of A be 5: (0.05～0.25);
Three, with the La that takes by weighing in the step 2
2O
3, SiO
2Place ball grinder with A, add absolute ethyl alcohol and abrading-ball, wet-milling mixes, and obtains mixture; Wherein the mass ratio of powder and absolute ethyl alcohol is 1: (0.5～3), the mass ratio of powder and abrading-ball are 1: (3～5); The quality of powder is meant La
2O
3, SiO
2Gross mass with A;
Four, behind the mixture oven dry that step 3 is obtained, mistake 160～500 mesh sieves, the temperature lower calcination 5～15h at 1473～1673K obtains calcining powder;
Five, the calcining powder cold moudling under the pressure of 10～40MPa that step 4 is obtained, cold isostatic compaction under 100～400MPa again, the dwell time is 3～10min, obtains base substrate;
Six, be under the condition of 1773～1973K in temperature with the base substrate that obtains in the step 5, sintering 5～30h obtains indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
The beneficial effect of this execution mode is:
1, compare with sol-gal process, the employed cost of material of this execution mode is low, and preparation technology is simple, and the cycle is short;
2, doping oxide has reduced required sintering temperature of high-temperature solid phase reaction method and temperature retention time, thereby has reduced energy consumption;
3, doping oxide has reduced by second phase content, has improved the density of oxygen base apatite-type lanthanum silicate solid electrolyte material;
4, compare with doped with oxygen base apatite-type lanthanum silicate solid electrolyte not; (873～1073K) conductivity is doubled many, helps improving the useful life of SOFC under middle low temperature for indium that this execution mode synthesized or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte.
Embodiment three: what this execution mode and embodiment two were different is: in the step 1 with 150～250Kh
-1Programming rate be warming up to 973～1173K, the insulation 2～3h.Other is identical with embodiment two.
Embodiment four: what this execution mode was different with embodiment two or three is: in the step 1 with 200～400Kh
-1Cooling rate reduce to room temperature.Other is identical with embodiment two or three.
Embodiment five: what this execution mode was different with one of embodiment two to four is: La in the step 2
2O
3With SiO
2The ratio of amount of substance be 5: (5.6～5.8), La
2O
3With the ratio of the amount of substance of A be 5: (0.10～0.20).Other is identical with one of embodiment two to four.
Embodiment six: what this execution mode was different with one of embodiment two to five is: in the step 3, and with the rotating speed of 300～400rpm, wet-milling 12～48h.Other is identical with one of embodiment two to five.
Embodiment seven: what this execution mode was different with one of embodiment two to six is: the mixture that in the step 4 step 3 is obtained is dried 12～48h in the baking oven of 373～393K.Other is identical with one of embodiment two to six.
Embodiment eight: what this execution mode was different with one of embodiment two to seven is: in the step 4, after the mixture oven dry that step 3 is obtained, cross 200～400 mesh sieves, the temperature lower calcination 8～12h at 1573～1673K obtains calcining powder.Other is identical with one of embodiment two to seven.
Embodiment nine: what this execution mode was different with one of embodiment two to eight is: in the step 5, and cold isostatic compaction under 200～300MPa, the dwell time is 5～8min, obtains base substrate.Other is identical with one of embodiment two to eight.
Embodiment ten: what this execution mode was different with one of embodiment two to nine is: in the step 6; With the base substrate that obtains in the step 5 is under the condition of 1773～1873K in temperature; Sintering 10～20h obtains indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.Other is identical with one of embodiment two to nine.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment one:
The preparation method of present embodiment indium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3, SiO
2And In
2O
3Place three crucibles respectively, again crucible is placed high temperature furnace, with 100Kh
-1Programming rate be warming up to 1173K, the insulation 3h after, with 100Kh
-1Cooling rate reduce to room temperature;
Two, take by weighing the La that 30g handles through step 1
2O
3, the SiO that handles through step 1 of 6.09g
2With the In of 1.28g through the step 1 processing
2O
3
Three, with the La that takes by weighing in the step 2
2O
3, SiO
2And In
2O
3Place ball grinder, add 30mL absolute ethyl alcohol and zirconium oxide balls, the speed wet-milling 24h with 400rpm obtains mixture; Wherein the mass ratio of oxide powder and zirconium oxide balls is 1: 3;
Four, the mixture that step 3 is obtained in the 393K baking oven dry 12h, then cross 160 mesh sieves after, in the air furnace of 1623K, calcine 10h, obtain calcining powder;
Five, the calcining powder cold moudling under the pressure of 20MPa that step 4 is obtained, cold isostatic compaction under 200MPa again, the dwell time is 5min, obtains base substrate;
Six, be under the condition of 1923K in temperature with the base substrate that obtains in the step 5, pressureless sintering 10h obtains indium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
Embodiment two:
The preparation method of present embodiment niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3, SiO
2And Nb
2O
5Place three crucibles respectively, again crucible is placed high temperature furnace, with 100Kh
-1Programming rate be warming up to 1173K, the insulation 3h after, with 100Kh
-1Cooling rate reduce to room temperature;
Two, take by weighing the La that 15g handles through step 1
2O
3, the SiO that handles through step 1 of 3.04g
2With the Nb of 0.61g through the step 1 processing
2O
5
Three, with the La that takes by weighing in the step 2
2O
3, SiO
2And Nb
2O
5Place ball grinder, add 15mL absolute ethyl alcohol and zirconium oxide balls, the speed wet-milling 24h with 400rpm obtains mixture; Wherein the mass ratio of oxide powder and zirconium oxide balls is 1: 3;
Four, the mixture that step 3 is obtained in the 393K baking oven dry 12h, then cross 160 mesh sieves after, in the air furnace of 1623K, calcine 10h, obtain calcining powder;
Five, the calcining powder cold moudling under the pressure of 20MPa that step 4 is obtained, cold isostatic compaction under 200MPa again, the dwell time is 5min, obtains base substrate;
Six, be under the condition of 1923K in temperature with the base substrate that obtains in the step 5, pressureless sintering 10h obtains niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
Contrast test one:
The preparation method of this test oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3And SiO
2Place two crucibles respectively, again crucible is placed high temperature furnace, with 100Kh
-1Programming rate be warming up to 1173K, the insulation 3h after, with 100Kh
-1Cooling rate reduce to room temperature;
Two, take by weighing the La that 16.38g handles through step 1
2O
3With the SiO of 3.62g through the step 1 processing
2
Three, with the La that takes by weighing in the step 2
2O
3And SiO
2Place ball grinder, add 20mL absolute ethyl alcohol and zirconium oxide balls, the speed wet-milling 24h with 400rpm obtains mixture; Wherein the mass ratio of oxide powder and zirconium oxide balls is 1: 3;
Four, the mixture that step 3 is obtained in the 393K baking oven dry 12h, then cross 160 mesh sieves after, in the air furnace of 1623K, calcine 10h, obtain calcining powder;
Five, the calcining powder cold moudling under the pressure of 20MPa that step 4 is obtained, cold isostatic compaction under 100～400MPa again, the dwell time is 5min, obtains base substrate;
Six, be under the condition of 1923K in temperature with the base substrate that obtains in the step 5, pressureless sintering 10h obtains oxygen base apatite-type lanthanum silicate solid electrolyte material.
Fig. 1 is the unadulterated La that contrast test one is synthesized
10Si
6O
27XRD spectra, peak position shown in " ο " is the second phase La
2SiO
5Characteristic peak.
Fig. 2 is embodiment one products therefrom La
10Si
5.5In
0.5O
26.75XRD spectra; Fig. 3 is embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25XRD spectra.
Can find out that from XRD spectra Fig. 2 and Fig. 3 peak type are sharp-pointed, and product La is described
10Si
5.5In
0.5O
26.75And La
10Si
5.5Nb
0.5O
27.25Have oxygen base apatite structure, simultaneously, the second phase diffraction maximum disappears, and explains through the doping of indium and niobium, has obviously reduced by second phase content.
Fig. 4 is embodiment one products therefrom La
10Si
5.5In
0.5O
26.75The AC impedance spectrogram; Visible by Fig. 4, product has less crystal grain impedance and crystal boundary impedance; Fig. 5 is embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25The AC impedance spectrogram; Visible by Fig. 5, product has less crystal grain impedance and crystal boundary impedance.
Fig. 6 is a total conductivity Arrhenius curve, and wherein " ο " represents embodiment one products therefrom La
10Si
5.5In
0.5O
26.75Total conductivity Arrhenius curve,
Represent embodiment two products therefrom La
10Si
5.5Nb
0.5O
27.25Total conductivity Arrhenius curve, " " represents the synthetic unadulterated La of contrast test one
10Si
6O
27Total conductivity Arrhenius curve.As can be seen from the figure, through doped indium and niobium, the conductivity of oxygen base apatite-type lanthanum silicate solid electrolyte obviously improves.When 1073K, La
10Si
5.5In
0.5O
26.75Conductivity be 1.75 * 10
-2Scm
-1, La
10Si
5.5Nb
0.5O
27.25Conductivity be 1.23 * 10
-2Scm
-1, apparently higher than unadulterated lanthanum silicate La
10Si
6O
27Conductivity 5.84 * 10
-3Scm
-1
Claims (10)
1. indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that the chemical formula of indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is La
10Si
6-xIn
xO
27-x/2Or La
10Si
6-xNb
xO
27+x/2, wherein, the span of x is 0＜x≤2.
2. the preparation method of indium as claimed in claim 1 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that the preparation method of indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material carries out according to the following steps:
One, with oxide powder La
2O
3, SiO
2Place three crucibles respectively with A, again crucible is placed high temperature furnace, with 100～300Kh
-1Programming rate be warming up to 873～1273K, the insulation 1～4h after, with 100～500Kh
-1Cooling rate reduce to room temperature; Wherein A represents In
2O
3Or Nb
2O
5
Two, take by weighing the La that handles through step 1
2O
3, SiO
2And A, wherein La
2O
3With SiO
2The ratio of amount of substance be 5: (5.5～5.9), La
2O
3With the ratio of the amount of substance of A be 5: (0.05～0.25);
Three, with the La that takes by weighing in the step 2
2O
3, SiO
2Place ball grinder with A, add absolute ethyl alcohol and abrading-ball, wet-milling mixes, and obtains mixture; Wherein the mass ratio of powder and absolute ethyl alcohol is 1: (0.5～3), the mass ratio of powder and abrading-ball are 1: (3～5); The quality of powder is meant La
2O
3, SiO
2Gross mass with A;
Four, behind the mixture oven dry that step 3 is obtained, mistake 160～500 mesh sieves, the temperature lower calcination 5～15h at 1473～1673K obtains calcining powder;
Five, the calcining powder cold moudling under the pressure of 10～40MPa that step 4 is obtained, cold isostatic compaction under 100～400MPa again, the dwell time is 3～10min, obtains base substrate;
Six, be under the condition of 1773～1973K in temperature with the base substrate that obtains in the step 5, sintering 5～30h obtains indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
3. the preparation method of indium according to claim 2 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that in the step 1 with 150～250Kh
-1Programming rate be warming up to 973～1173K, the insulation 2～3h.
4. the preparation method of indium according to claim 3 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that in the step 1 with 200～400Kh
-1Cooling rate reduce to room temperature.
5. according to the preparation method of claim 3 or 4 described indiums or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material, it is characterized in that La in the step 2
2O
3With SiO
2The ratio of amount of substance be 5: (5.6～5.8), La
2O
3With the ratio of the amount of substance of A be 5: (0.10～0.20).
6. the preparation method of indium according to claim 2 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that in the step 3, with the rotating speed of 300～400rpm, and wet-milling 12～48h.
7. the preparation method of indium according to claim 6 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material, the mixture that it is characterized in that in the step 4 step 3 being obtained is dried 12～48h in the baking oven of 373～393K.
8. according to the preparation method of claim 6 or 7 described indiums or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material; It is characterized in that in the step 4; After the mixture oven dry that step 3 is obtained; Cross 200～400 mesh sieves, the temperature lower calcination 8～12h at 1573～1673K obtains calcining powder.
9. the preparation method of indium according to claim 8 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material is characterized in that in the step 5, cold isostatic compaction under 200～300MPa, and the dwell time is 5～8min, obtains base substrate.
10. the preparation method of indium according to claim 9 or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material; It is characterized in that in the step 6; With the base substrate that obtains in the step 5 is under the condition of 1773～1873K in temperature; Sintering 10～20h obtains indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| CN108493470A (en) * | 2018-03-21 | 2018-09-04 | 辽宁工业大学 | A kind of solid electrolyte and preparation method thereof of the compound regulation and control of vacancy/interstitial oxygen concentration |
| CN109713346A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position |
| CN114171787A (en) * | 2021-12-07 | 2022-03-11 | 四川大学 | Mg2+Doped and modified NASCION type sodium ion solid electrolyte and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101615679A (en) * | 2009-07-29 | 2009-12-30 | 华南理工大学 | Vanadium-doped in lanthanum site apatite-type lanthanum silicate solid electrolyte and preparation method thereof |
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2012
- 2012-06-05 CN CN2012101827968A patent/CN102709578A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101615679A (en) * | 2009-07-29 | 2009-12-30 | 华南理工大学 | Vanadium-doped in lanthanum site apatite-type lanthanum silicate solid electrolyte and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ATSUSHI MINESHIGE,ET AL: "Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes", 《SOLID STATE IONICS》, no. 192, 6 November 2010 (2010-11-06) * |
| YU-LIN KU,ET AL.: "Assessment of thermochemically stable apatite La10(SiO4)6O3 as electrolyte for solid oxide fuel cells", 《CERAMICS INTERNATIONAL》, no. 38, 27 January 2012 (2012-01-27) * |
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| CN103199287A (en) * | 2013-04-14 | 2013-07-10 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| CN103199287B (en) * | 2013-04-14 | 2014-11-19 | 北京科技大学 | Method for promoting densification of silicon-based apatite through doping Cu |
| CN109713346A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Adulterate apatite-type lanthanum silicate and its preparation method and application in silicon position |
| CN108493470A (en) * | 2018-03-21 | 2018-09-04 | 辽宁工业大学 | A kind of solid electrolyte and preparation method thereof of the compound regulation and control of vacancy/interstitial oxygen concentration |
| CN114171787A (en) * | 2021-12-07 | 2022-03-11 | 四川大学 | Mg2+Doped and modified NASCION type sodium ion solid electrolyte and preparation method thereof |
| CN114171787B (en) * | 2021-12-07 | 2024-04-16 | 四川大学 | Mg (magnesium) 2+ Doped modified NASCION sodium ion solid electrolyte and preparation method thereof |
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