CN101692495A - Laser synthesis method of LaGaO3 based solid electrolyte - Google Patents
Laser synthesis method of LaGaO3 based solid electrolyte Download PDFInfo
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Abstract
The invention discloses a laser synthesis method of LaGaO3 based solid electrolyte. Laser beams are utilized for direct heating to generate the material components of LaGaO3 based solid electrolyte, and the raw materials react in a laser molten pool to generate electrolyte and then is cooled down and solidified. In the invention, a laser sintering rapid synthesis method is utilized to prepare the LaGaO3 based solid electrolyte, the reaction process is simple, the sintering speed is high, tens of grams of samples can be sintered completely in a few seconds, high temperature formed by the high energy of laser beams causes the raw materials to react under a melting state, the reaction of raw materials is very adequate, products manufactured by the laser sintering method has high purity, cooling and solidification are carried out after reaction, therefore, produced products have very high density, and the electrical behavior is very superior.
Description
Technical field
The invention belongs to the Solid Oxide Fuel Cell technical field, a kind of preparation laser synthesis method of LaGaO 3 based solid electrolyte particularly is provided.
Background technology
Solid Oxide Fuel Cell, has the transformation efficiency height, characteristics such as environmental pollution is little, and fuel source is abundant are considered to the cleaning of 21 century first-selection, generation technology efficiently, but with regard to present situation, the Solid Oxide Fuel Cell technology does not also reach the requirement of commercial applications on performance, life-span and cost, exist the problem that some wait to solve, as the selection difficulty of material, complicated process of preparation, cost are high excessively.What generally adopt at present is that zirconia (YSZ) with stabilized with yttrium oxide is electrolytical high temperature modification solid oxide fuel battery system, because the ionic conductivity of YSZ is lower, need under the high temperature about 800-1000 ℃, move, this has increased the difficulty in the selection of battery and system support material and preparation, increased the operating cost of system, and engineering problems such as long-time running stability have been brought, limited the further developing and using of high temperature solid oxide fuel cell [George et al.J Power Sources, 71 (1998) 131-137].If can make the operating temperature of Solid Oxide Fuel Cell be reduced to 600-800 ℃, not only can select cheap material for use, improve the stability of battery, extend the life of a cell, the more important thing is the scale and the civil nature that help Solid Oxide Fuel Cell.For operating temperature being reduced to below 800 ℃, must studying and explore at 600-800 ℃ of novel electrolytes material that has than high ionic conductivity.The lanthanum gallate series material that discovery Sr, Mg such as Ishihara in 1994 mix (being called for short LSGM) presents the ionic conductivity higher than YSZ at middle warm area (600-800 ℃), under 800 ℃ in the very wide partial pressure of oxygen scope ionic conductivity all at 0.10S cm
-1About [Ishihara T et al.JAm Chem Soc, 1994,116 (9): 3801].So superior electrical property and good stable makes it become a kind of desirable electrolyte of intermediate temperature solid oxide fuel cell.
LaGaO
3The synthetic method that based solid electrolyte is commonly used mainly contains high-temperature solid phase reaction method [E.Gomes et al.Solid State Ionics 179 (2008) 1325-1328] and wet chemistry method [CN02126556.9; ZL200710176457.8; Fujita et al.United States, US006337006B1].Two kinds of methods all respectively have its characteristics, particularly all have very big-difference at aspects such as preparing electrolytical one-tenth phase temperature, granular size, density, microstructure and conductivity.(2-3 days) could become phase fully will to be incubated the sufficiently long time at (about 1550 ℃) under the very high sintering temperature with solid reaction process synthesis of solid electrolyte, and it is big and be difficult to shortcoming such as sintering densification that synthetic sample has a particle.Adopt wet chemical method can effectively reduce the one-tenth phase temperature of electrolyte; but but exist preparation condition to be difficult to control; be prone to the segregation of metal ion and be not suitable for the problem of large-scale production; simultaneously owing to the mutually stable ratio range of perovskite is very narrow; therefore all can cause second mutually the generation with stoichiometric(al) departing from a little, so prepare quite difficulty of pure LSGM.Generally speaking, be that conventional high-temperature solid reaction process or liquid phase method obtain all unusual difficulties of highly purified LSGM solid electrolyte, and length consuming time, preparation cost height.
Summary of the invention
The object of the present invention is to provide a kind of laser synthesis method of LaGaO 3 based solid electrolyte, this method technology is simple, and sintering purity height, speed are fast, and suitable serialization, large-scale production.
The present invention is by the following technical solutions: a kind of laser synthesis method of LaGaO 3 based solid electrolyte, can generate the electrolytical raw material composition of LaGaO 3 based solid by the direct heating of laser beam, raw material be reacted in laser molten pool generate electrolyte and cooled and solidified.
Adopt 5KW CO
2Gas laser or Nd:YAG solid state laser, the technological parameter of LASER HEATING process is: optical maser wavelength is 10.6 μ m, and power density is 1.0-1.2kW/cm
2, beam flying speed is 0.6-3mm/s.
The electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-yMg
yO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio be
The electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-yMg
Y-zM
zO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3,0＜z＜y, M are Cr, Mn, Fe, Co or Ni, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO, M
2O
3Mol ratio be
The electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-y-zM
zMg
yO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3,0＜z＜(1-y), M is Cr, Mn, Fe, Co or Ni, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO, M
2O
3Mol ratio be
The present invention adopts laser sintered quick synthetic method to prepare the LaGaO 3 based solid electrolyte, course of reaction is simple, sintering velocity is fast, tens of gram samples can finish by sintering several seconds, and the high temperature that the high-energy of laser beam forms reacts raw material under molten condition, raw material reaction is very abundant, the product purity height that laser sintering processes is made, reaction back cooled and solidified makes the density that generates product quite high, relative density is up to 98.54%, it is the pottery that the layer of surface enamel is arranged with regular texture, high purity, high relative density improves conductivity of electrolyte materials greatly, conductivity in the time of 800 ℃ is up to 0.134S/cm, and these characteristics have determined the sample of laser Fast Sintering preparation to have excellent electric performance.Quick synthesizing of laser is a kind of technology of preparing of environmental protection simultaneously, and it can realize producing in batches by continuous scanning, thereby realizes scale, the automation of production.
Description of drawings
Fig. 1 is the La that embodiment 1 synthesizes
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δXRD figure;
Fig. 2 is the La that embodiment 2 synthesizes
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δXRD figure;
Fig. 3 is the La that embodiment 3 synthesizes
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δXRD figure;
Fig. 4 is the La that embodiment 4 synthesizes
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δXRD figure;
Fig. 5 is the La that embodiment 5 synthesizes
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δXRD figure;
Fig. 6 is the La that embodiment 6 synthesizes
0.8Sr
0.2Ga
0.83Mg
0.17O
3-δXRD figure;
Fig. 7 is the La that embodiment 7 synthesizes
0.7Sr
0.3Ga
0.7Mg
0.3O
3-δXRD figure;
Fig. 8 is the La of 0.1 mole of Cr of embodiment 8 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.07Cr
0.1O
3-δXRD figure;
Fig. 9 is the La of 0.1 mole of Mn of embodiment 9 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.07Mn
0.1O
3-δXRD figure;
Figure 10 is the La of 0.1 mole of Fe of embodiment 10 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.07Fe
0.1O
3-δXRD figure;
Figure 11 is the La of 0.1 mole of Ni of embodiment 11 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.07Ni
0.1O
3-δXRD figure;
Figure 12 is the La of 0.05 mole of Co of embodiment 12 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.12Co
0.05O
3-δXRD figure;
Figure 13 is the La of 0.1 mole of Co of embodiment 13 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.07Co
0.1O
3-δXRD figure;
Figure 14 is the La of 0.15 mole of Co of embodiment 14 synthetic Ga positions doping
0.8Sr
0.2Ga
0.83Mg
0.02Co
0.15O
3-δXRD figure;
Figure 15 is embodiment 2 synthetic La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δSEM figure.
Figure 16 is embodiment 2 synthetic La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δConductivity vary with temperature schematic diagram.
Embodiment
Embodiment 1: fixed laser wavelength 10.6 μ m, 1mm/s is constant for beam flying speed, at power density 1.0kW/cm
2Synthetic down La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δ(x=0.1, y=0.2) solid electrolyte:
La before the weighing
2O
3, Ga
2O
3With MgO 1000 ℃ of pre-burning 7h in stove, to decompose carbonate and hydroxide wherein, all the other raw materials can generate the electrolytical raw material of lanthanum gallate by La then at the dry 2h of drying box
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio 9: 2: 8: 4 take by weighing, in agate mortar, grind 1h, with sample dry 2h in drying box, be pressed into strip with hydraulic press, rectangular long 40mm, wide 5mm, the thick 5mm of being of a size of, rectangularly put into that measuring cup is built in order to avoid the efflorescence that absorbs water is carried out sintering with laser at last with what press.Fixed laser wavelength 10.6 μ m, beam flying speed are that 1mm/s is constant in sintering process, adopt power density 1.0kW/cm
2Carry out sintering, make press rectangular in laser molten pool reaction generate electrolyte and cooled and solidified becomes La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δ, the X-ray diffraction material phase analysis of product correspondence is seen Fig. 1, the XRD result of Fig. 1 shows and has formed pure La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δPhase.
Embodiment 2: be that with the difference of embodiment 1 power density is 1.1kW/cm
2, the La of formation
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δCorresponding X-ray diffraction material phase analysis is seen Fig. 2, and the XRD result of Fig. 2 shows and formed pure La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δPhase.Use scanning electron microscopic observation La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δMicrostructure, product La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δSEM figure as shown in figure 15, the La for preparing as can be seen
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δWell-regulated structure, dense structure, crystallite dimension is probably at 5-10 μ m; Adopt the method for ac impedance spectroscopy to test the conductivity of making product, product La with conductivity measurement
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δConductivity vary with temperature situation and see Figure 16, conductivity reaches 0.134S/cm 800 ℃ the time as can be seen.
Embodiment 3: be that with the difference of embodiment 1 power density is 1.2kW/cm
2, the La of formation
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δCorresponding X-ray diffraction material phase analysis is seen Fig. 3, and the XRD result of Fig. 3 shows and formed pure La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δPhase.
Embodiment 4: fixed power density 1.1kW/cm
2Constant, synthetic La under beam flying speed 3mm/s
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δSolid electrolyte:
La before the weighing
2O
3, Ga
2O
3With MgO 1000 ℃ of pre-burning 7h in stove, to decompose carbonate and hydroxide wherein, all the other raw materials can generate the electrolytical raw material of lanthanum gallate by La then at the dry 2h of drying box
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio 9: 2: 8: 4 take by weighing, and grind 1h in agate mortar, with sample dry 2h in drying box, are pressed into strip with hydraulic press, rectangular long 40mm, wide 5mm, the thick 5mm of being of a size of.Rectangularly put into that measuring cup is built in order to avoid the efflorescence that absorbs water is carried out sintering with laser at last with what press.Fixed laser wavelength 10.6 μ m, power density are 1.1kW/cm in sintering process
2Constant, adopt the beam flying speed of 3mm/s to carry out sintering, make press rectangular in laser molten pool reaction generate electrolyte and cooled and solidified becomes La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δ, the X-ray diffraction material phase analysis of product correspondence is seen Fig. 4, the XRD result of Fig. 4 show except have minute quantity second mutually, basically formed purer La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δPhase.
Embodiment 5: be that beam flying speed is 0.6mm/s, the La of formation with the difference of embodiment 4
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δCorresponding X-ray diffraction material phase analysis is seen Fig. 5, and the XRD result of Fig. 5 shows and formed pure La
0.9Sr
0.1Ga
0.8Mg
0.2O
3-δPhase.
Embodiment 6: adopting optical maser wavelength 10.6 μ m, power density is 1.1kW/cm
2, beam flying speed is the lanthanum gallate series material of the synthetic different proportionings of 1mm/s: La
0.8Sr
0.2Ga
0.83Mg
0.17O
3-δ(x=0.2 y=0.17), is raw material La with the difference of embodiment 2
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio be 80: 40: 83: 34, corresponding X-ray diffraction material phase analysis is seen Fig. 6, the XRD result of Fig. 6 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.17O
3-δPhase.
Embodiment 7: adopting optical maser wavelength 10.6 μ m, power density is 1.1kW/cm
2, beam flying speed is the lanthanum gallate material of synthetic another proportioning of 1mm/s: La
0.7Sr
0.3Ga
0.7Mg
0.3O
3-δ(x=0.3 y=0.3), is raw material La with the difference of embodiment 6
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio be 7: 6: 7: 6, the X-ray diffraction material phase analysis of product correspondence is seen Fig. 7, the XRD result of Fig. 7 shows and has formed pure La
0.7Sr
0.3Ga
0.7Mg
0.3O
3-δPhase.
Embodiment 8: adopting optical maser wavelength 10.6 μ m, power density is 1.1kW/cm
2, beam flying speed is the lanthanum gallate sample of the synthetic Ga position of 1mm/s containing transition metal element, existing La with doping Cr
0.8Sr
0.2Ga
0.83Mg
0.07Cr
0.1O
3-δ(z=0.10) for example its implementation process is described:
La before the weighing
2O
3, Ga
2O
3With MgO 1000 ℃ of pre-burning 7h in stove, to decompose carbonate and hydroxide wherein, all the other raw materials can generate electrolyte La then at the dry 2h of drying box
0.8Sr
0.2Ga
0.83Mg
0.07Cr
0.1O
3-δRaw material La
2O
3, SrCO
3, Ga
2O
3, MgO, Cr
2O
3By 80: 40: 83: 14: 10 mol ratio took by weighing, and ground 2h in agate mortar, with sample dry 2h in drying box, was pressed into strip with hydraulic press, rectangular long 40mm, wide 5mm, the thick 5mm of being of a size of.Rectangularly put into that measuring cup is built in order to avoid the efflorescence that absorbs water is carried out sintering with laser at last with what press.In sintering process, fixed laser wavelength 10.6 μ m, power density are 1.1kW/cm
2, the constant sintering that carries out of beam flying speed 1mm/s, make press rectangular in laser molten pool reaction generate electrolyte and cooled and solidified becomes La
0.8Sr
0.2Ga
0.83Mg
0.07Cr
0.1O
3-δ, the X-ray diffraction material phase analysis of product correspondence is seen Fig. 8, the XRD result of Fig. 8 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.07Cr
0.1O
3-δPhase.
Embodiment 9: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the lanthanum gallate sample of the synthetic Ga position containing transition metal element M n of 1mm/s: La
0.8Sr
0.2Ga
0.83Mg
0.07Mn
0.1O
3-δ(z=0.10), the difference with embodiment 8 is the raw materials used La that is
2O
3, SrCO
3, Ga
2O
3, MgO and Mn
2O
3, the mol ratio of their correspondences is 80: 40: 83: 14: 10, the X-ray diffraction material phase analysis of product correspondence was seen Fig. 9, the XRD result of Fig. 9 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.07Mn
0.1O
3-δPhase.
Embodiment 10: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the lanthanum gallate sample of the synthetic Ga position of 1mm/s containing transition metal element of Fe: La
0.8Sr
0.2Ga
0.83Mg
0.07Fe
0.1O
3-δ(z=0.10), the difference with embodiment 8 is the raw materials used La that is
2O
3, SrCO
3, Ga
2O
3, MgO and Fe
2O
3, the mol ratio of their correspondences is 80: 40: 83: 14: 10, the X-ray diffraction material phase analysis of product correspondence was seen Figure 10, the XRD result of Figure 10 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.07Fe
0.1O
3-δPhase.
Embodiment 11: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the lanthanum gallate sample of the synthetic Ga position containing transition metal element Ni of 1mm/s: La
0.8Sr
0.2Ga
0.83Mg
0.07Ni
0.1O
3-δ(z=0.10), the difference with embodiment 8 is the raw materials used La that is
2O
3, SrCO
3, Ga
2O
3, MgO and Ni
2O
3, the mol ratio of their correspondences is 80: 40: 83: 14: 10, the X-ray diffraction material phase analysis of product correspondence was seen Figure 11, the XRD result of Figure 11 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.07Ni
0.1O
3-δPhase.
Embodiment 12: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the lanthanum gallate sample of the synthetic Ga position doping different content Co of 1mm/s: La
0.8Sr
0.2Ga
0.83Mg
0.17-zCo
zO
3-δ, existing with La
0.8Sr
0.2Ga
0.83Mg
0.12Co
0.05O
3-δ(z=0.05) for example its implementation process is described:
La before the weighing
2O
3, Ga
2O
3With MgO 1000 ℃ of pre-burning 7h in stove, to decompose carbonate and hydroxide wherein, all the other raw materials can generate the electrolytical raw material La of lanthanum gallate then at the dry 2h of drying box
2O
3, SrCO
3, Ga
2O
3, MgO, Co
2O
3By 80: 40: 83: 24: 5 mol ratio took by weighing, and ground 2h in agate mortar, with sample dry 2h in drying box, was pressed into strip with hydraulic press, rectangular long 40mm, wide 5mm, the thick 5mm of being of a size of.Rectangularly put into that measuring cup is built in order to avoid the efflorescence that absorbs water is carried out sintering with laser at last with what press.In sintering process, fixed laser wavelength 10.6 μ m, power density are 1.1kW/cm
2, the constant sintering that carries out of beam flying speed 1mm/s, make press rectangular in laser molten pool reaction generate electrolyte and cooled and solidified becomes La
0.8Sr
0.2Ga
0.83Mg
0.12Co
0.05O
3-δ, the X-ray diffraction material phase analysis of product correspondence is seen Figure 12, the XRD result of Figure 12 shows and has formed pure La
0.8Sr
0.2Ga
0.83Mg
0.12Co
0.05O
3-δPhase.
Embodiment 13: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the synthetic Ga position of the 1mm/s lanthanum gallate sample of another proportioning Co: the La that mixes
0.8Sr
0.2Ga
0.83Mg
0.07Co
0.1O
3-δ(z=0.1), be raw materials used La with embodiment 12 differences
2O
3, SrCO
3, Ga
2O
3, MgO, Co
2O
3Mol ratio be 80: 40: 83: 14: 10, the X-ray diffraction material phase analysis of product correspondence was seen Figure 13, and the XRD result of Figure 13 shows and formed pure La
0.8Sr
0.2Ga
0.83Mg
0.07Co
0.1O
3-δPhase.
Embodiment 14: optical maser wavelength 10.6 μ m, power density are 1.1kW/cm
2, beam flying speed is the synthetic Ga position of the 1mm/s lanthanum gallate sample of another proportioning Co: the La that mixes
0.8Sr
0.2Ga
0.83Mg
0.02Co
0.15O
3-δ(z=0.15), be raw materials used La with embodiment 12 differences
2O
3, SrCO
3, Ga
2O
3, MgO, Co
2O
3Mol ratio be 80: 40: 83: 4: 15, the X-ray diffraction material phase analysis of product correspondence was seen Figure 14, and the XRD result of Figure 14 shows and formed purer La
0.8Sr
0.2Ga
0.83Mg
0.02Co
0.15O
3-δPhase.
Employed laser is the 5kW CO that Wuhan unity laser company produces among the above embodiment
2Laser.Employed X-ray diffractometer is X ' the Pert PRO X-ray diffractometer that Holland produces among the embodiment 2, ESEM is the JSM-6700F ESEM that Japan produces, and conductivity measurement is the Pastat 2273 electrochemical impedance testers that U.S. PrincetonApplied Research produces.
Claims (5)
1. a laser synthesis method of LaGaO 3 based solid electrolyte is characterized in that: can generate the electrolytical raw material composition of LaGaO 3 based solid by the direct heating of laser beam, raw material be reacted in laser molten pool generate electrolyte and cooled and solidified.
2. laser synthesis method of LaGaO 3 based solid electrolyte as claimed in claim 1 is characterized in that: adopt 5KW CO
2Gas laser or Nd:YAG solid state laser, the technological parameter of LASER HEATING process is: optical maser wavelength is 10.6 μ m, and power density is 1.0-1.2kW/cm
2, beam flying speed is 0.6-3mm/s.
3. laser synthesis method of LaGaO 3 based solid electrolyte as claimed in claim 1 or 2 is characterized in that: the electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-yMg
yO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO mol ratio be
4. laser synthesis method of LaGaO 3 based solid electrolyte as claimed in claim 1 or 2 is characterized in that: the electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-yMg
Y-zM
zO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3,0＜z＜y, M are Cr, Mn, Fe, Co or Ni, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO, M
2O
3Mol ratio be
5. laser synthesis method of LaGaO 3 based solid electrolyte as claimed in claim 1 or 2 is characterized in that: the electrolytical molecular formula of described LaGaO 3 based solid is La
1-xSr
xGa
1-y-zM
zMg
yO
3-δ, 0＜x in the molecular formula≤0.3,0＜y≤0.3,0＜z＜(1-y), M is Cr, Mn, Fe, Co or Ni, raw materials used La
2O
3, SrCO
3, Ga
2O
3, MgO, M
2O
3Mol ratio be
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910066223A CN101692495A (en) | 2009-10-22 | 2009-10-22 | Laser synthesis method of LaGaO3 based solid electrolyte |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928138A (en) * | 2010-09-01 | 2010-12-29 | 郑州大学 | Laser synthesis method of CaTiO3-CaTiSiO5 |
| WO2011130926A1 (en) * | 2010-04-23 | 2011-10-27 | 海洋王照明科技股份有限公司 | Rare earth ion doped lanthanum gallate luminous material containing metal particles and preparation method thereof |
| CN106495208A (en) * | 2016-11-14 | 2017-03-15 | 东北大学 | A kind of lanthanum gallate amorphous and preparation method thereof |
| CN108598562A (en) * | 2018-03-27 | 2018-09-28 | 电子科技大学 | A kind of heat treatment method and lithium cell structure of solid electrolyte film |
| CN110429332A (en) * | 2019-09-06 | 2019-11-08 | 深圳先进技术研究院 | A kind of preparation method of inorganic solid electrolyte piece |
| CN115028446A (en) * | 2022-05-16 | 2022-09-09 | 广州小鹏汽车科技有限公司 | Solid electrolyte, preparation method thereof, secondary battery and electric automobile |
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2009
- 2009-10-22 CN CN200910066223A patent/CN101692495A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011130926A1 (en) * | 2010-04-23 | 2011-10-27 | 海洋王照明科技股份有限公司 | Rare earth ion doped lanthanum gallate luminous material containing metal particles and preparation method thereof |
| US8821759B2 (en) | 2010-04-23 | 2014-09-02 | Ocean's King Lighting Science & Technology Co., Ltd. | Rare earth ion doped lanthanum gallate luminous material containing metal particles and preparation method thereof |
| CN101928138A (en) * | 2010-09-01 | 2010-12-29 | 郑州大学 | Laser synthesis method of CaTiO3-CaTiSiO5 |
| CN106495208A (en) * | 2016-11-14 | 2017-03-15 | 东北大学 | A kind of lanthanum gallate amorphous and preparation method thereof |
| CN108598562A (en) * | 2018-03-27 | 2018-09-28 | 电子科技大学 | A kind of heat treatment method and lithium cell structure of solid electrolyte film |
| CN110429332A (en) * | 2019-09-06 | 2019-11-08 | 深圳先进技术研究院 | A kind of preparation method of inorganic solid electrolyte piece |
| CN115028446A (en) * | 2022-05-16 | 2022-09-09 | 广州小鹏汽车科技有限公司 | Solid electrolyte, preparation method thereof, secondary battery and electric automobile |
| CN115028446B (en) * | 2022-05-16 | 2024-03-08 | 广州小鹏汽车科技有限公司 | Solid electrolyte, preparation method thereof, secondary battery and electric automobile |
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