CN1323920A - Prepn. of nanometer crystal film of rare earth doped ZrO2 solid electrolyte - Google Patents
Prepn. of nanometer crystal film of rare earth doped ZrO2 solid electrolyte Download PDFInfo
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- CN1323920A CN1323920A CN 01109841 CN01109841A CN1323920A CN 1323920 A CN1323920 A CN 1323920A CN 01109841 CN01109841 CN 01109841 CN 01109841 A CN01109841 A CN 01109841A CN 1323920 A CN1323920 A CN 1323920A
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Abstract
A preparing method of solid electrolyte nanometer crystal thin film by rare-earth doping zirconium dioxide uses rare-earth mineral salt and zirconium mineral salt as a raw material, polyethylene glycol as an agant for forming the film, ethanol and water mixing solution as a dispersing agent to make the coating liquid. The desirecd thickness of the thin film fill be obtained by repeated coating the single-crystal silicon or quartz base chip with the liquid. After annealing the thin film, the final thin film product of solid electrolyte nanometer crystal of rare-earth doping with zirconium dioxide has been produced with the advantages of plane surface, no gap and even granule compactness.
Description
The invention belongs to the new energy materials field, particularly a kind of preparation method who applies the preparation nanometer crystal film of rare earth doped ZrO 2 solid electrolyte with the sol-gel rotation.
Rear-earth-doped solid electrolyte material is widely used in aspects such as chemical sensor, high technology ceramics and electrode materials, its prior potential application be used for field of solid oxide fuel (Solid Oxide Fuel Cell, SOFC).Fuel cell is a kind of novel battery that directly ignition energy is converted into electric energy; because it does after fuel, the fuel combustion pollution-free and have a very high energy transformation ratio with hydrogen, Sweet natural gas, methyl alcohol, ethanol and other hydrocarbon polymer etc.; and be considered to one of new forms of energy of 21 century, be significant to overcoming the human energy dilemma that is faced.SOFC is all solid stateization of the third generation fuel cell that grows up behind phosphoric acid salt fuel cell and fused carbonate type fuel cell.Compare with other fuel cells, it have high reliability, high energy quality than and energy volume ratio, simple structure and pollution advantage such as lack, thereby become the competitively key object of R and D of western developed country.
As a key member, the quality of solid oxide electrolytic film material directly influences the generating efficiency and the life-span of fuel cell, and therefore, the preparation technology of exploitation high-quality thin film material is just indispensable.In order to reduce the service temperature of SOFC, should reduce the thickness of electrolytic thin-membrane as far as possible, preparing thickness becomes a new direction of such investigation of materials gradually less than the solid electrolyte nano-crystal film of 10 μ m, controlled, the surperficial even compact of grain-size, conductivity excellence.At present, the zirconium white system that rear-earth-doped zirconium white, particularly yttrium oxide (or Scium trioxide) are stable, higher and become the main electrolyte film material of state SOFC such as U.S., day research with its specific conductivity under service temperature.For example, U.S. Pat 5494700 has just been put down in writing the method that a kind of preparation is used for the assembly of Solid Oxide Fuel Cell, comprising apply the polycrystalline metal oxide film on matrix.
Prior art adopts methods such as spray pyrolysis, electrochemistry vapor deposition, plasma body splash to prepare thin-film material usually.Compare with aforesaid method, the sol-gel that development in recent years is got up (Sol-gel) method can prepare film (＜2 μ m) even, densification (not having be full of cracks, free of pinholes) because of having, and can become the advantage of phase under lower temperature, and receive much attention.
The object of the present invention is to provide a kind of preparation method of nanometer crystal film of rare earth doped ZrO 2 solid electrolyte, be used at rear-earth-doped zirconia solid electrolyte nano-crystal film than various binary of preparation or ternary doping under the low temperature thermal oxidation.
Preparation method of the present invention is: with inorganic salt of rare earth and zirconium inorganic salt is raw material, and the amount beguine of the two is decided according to prepared film, and polyoxyethylene glycol is a membrane-forming agent, and ethanol/water mixed solvent is a dispersion agent, makes and is coated with stain liquid.Control applies and dried glue decomposition condition, by repeatedly applying, promptly repeats coating, oven dry and presintering on silicon single crystal or quartz substrate, makes the film of desired thickness.After this film annealed at a certain temperature, can get the good nano-crystal film of crystallization.
Described inorganic salt of rare earth comprises rare earth nitrate and rare earth chloride.Rare earth element is respectively elements such as scandium, yttrium lanthanum, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.The zirconium inorganic salt comprise Zircosol ZN and basic zirconium chloride.The molecular weight of used polyoxyethylene glycol is 10000-40000.
In the raw material of forming by inorganic salt of rare earth and zirconium inorganic salt, can also further add al inorganic salt or Ti-inorganic salt.
Used al inorganic salt is aluminum nitrate or aluminum chloride.Used Ti-inorganic salt is titanous chloride.
The described stain liquid that is coated with consists of: water and alcoholic acid volume ratio are 1: 5-1: between 8, PEG concentration is between 20mg/ml～80mg/ml, and concentration of metal ions (said metal comprises rare earth, zirconium, aluminium or titanium) is between 0.05mol/1～0.2mol/L.The optimal set that is coated with stain liquid becomes: water and alcoholic acid volume ratio are 1: 8, and PEG concentration equals 40mg/ml, and concentration of metal ions is 0.10mol/l.
The rotation coating method is adopted in described coating, and the condition that rotation applies is rotating speed 3000～5000rpm, and rotational time is 5～25 seconds.Also can adopt other coating method, apply as slurry.Oven dry is that gel was dried 10～30 minutes down at 110 ℃, promptly gets dried glue.Presintering is that the dried glue that will obtain decomposes in 350～800 ℃ temperature range.As required, by repeating coating, oven dry, presintering, until the film that obtains desired thickness.
Described annealing temperature is 650～950 ℃.
Consisting of of the nano-crystal film of making by aforesaid method:
(ZrO
2)
1-x(RE
2O
3)
x,
Or (ZrO
2)
1-x-y(RE
2O
3)
x(Al
2O
3)
y,
Or (ZrO
2)
1-x-y(RE
2O
3)
x(TiO
2)
y,
Wherein:
(ZrO
2)
1-x(RE
2O
3)
xThe scope of middle x is 0.02～0.24, and RE can be two kinds of different rare earth elements; (ZrO
2)
1-x-y(RE
2O
3)
x(Al
2O
3)
yIn, when x=0.08, the scope of y is 0.02～0.20; (ZrO
2)
1-x-y(RE
2O
3)
x(TiO
2)
yIn, when x=0.12, the scope of y is 0.05～0.20.
The prepared rear-earth-doped solid electrolyte nano-crystal film that comes out of the present invention has surfacing, leakless, free of pinholes, the uniform particles densification, film thickness is 20-600nm, nanocrystalline grain size has potential using value at aspects such as intermediate temperature solid oxide fuel cells between 10-90nm.
Characteristics such as method of the present invention has simple to operate, and cost is low, and suitability is strong.Prepared film has surfacing, leakless, free of pinholes, uniform particles densification, phase is pure and the conductivity excellent characteristics.
Description of drawings:
Fig. 1. process flow sheet of the present invention;
Fig. 2. (ZrO
2)
0.92(Sc
2O
3)
0.08The one-tenth phase x-ray diffractogram of powder of film;
Fig. 3. (ZrO
2)
0.92(Sc
2O
3)
0.08The sem photograph on the cross section of film and surface;
Fig. 4. (ZrO
2)
0.92(Sc
2O
3)
0.08(a) and (ZrO
2)
0.92(Y
2O
3)
0.08(b) the atomic force microscope figure of film surface;
Fig. 5. (ZrO
2)
0.92(Sc
2O
3)
0.08Elementary composition (a) of film and depth profile (b) figure-Auger photoelectron spectrum;
Fig. 6. (ZrO
2)
0.92(Sc
2O
3)
0.08The impedance spectrum of film (c) and respective masses material (a, b) relatively.
Below in conjunction with embodiment technical scheme of the present invention is further described.Embodiment 1. (ZrO
2)
0.92(Sc
2O
3)
0.08Film
Accurately pipette Scium trinitrate and zirconium oxychloride solution, making its ratio in final oxide compound is required ZrO
2: Sc
2O
3It is 0.92: 0.08, add the water of calculated amount, thorough mixing reaction 1h under induction stirring, add polyoxyethylene glycol then, making its content in finally being coated with stain liquid is 40mg/ml, after PEG dissolves fully, add dehydrated alcohol to required water alcohol than being 1: 8, abundant again stirring reaction 1h, gained colloidal sol filters with double-deck quantitative paper at last.Be rotated coating in ultra-clean chamber, rotating speed is 4000rpm/min, and the time is 10 seconds.Transfer to immediately in about 110 ℃ baking oven through the film that is coated with stain, dried by the fire 20 minutes.Be transferred to after from baking oven, taking out in 400 ℃ the low temperature diffusion stove, feeding under an amount of oxygen atmosphere presintering 20 minutes.Film is through repeating to be coated with the operation of stain, oven dry and presintering, until 30 layers.Feeding under an amount of oxygen atmosphere, film is carried out sintering at last at 500-950 ℃.The gained film has the characteristics of surfacing, leakless, free of pinholes, uniform particles densification.
(ZrO
2)
0.92(Sc
2O
3)
0.08Film is beginning into phase more than 600 ℃, and temperature is high more, and Cheng Xiangyue is complete, 800 ℃ of 2 hours fluorite structure cube phase (see figure 2)s of Cheng Chun fully of annealing down, and becomes the phase temperature lower more than 700 ℃ than respective masses material.The thickness of film is that 0.6 μ m (sees Fig. 3 a).The particle mean size (is seen Fig. 3 b and Fig. 4 a) between 50-60nm.The composition of nano-crystal film is distributed in very even (see figure 5) in the degree of depth of 75-500nm.At (ZrO
2)
0.92(RE
2O
3)
0.08In the nano-crystal film, observed that the grain boundary resistance relevant with interfacial effect significantly reduces and the electricity that produces is led the reinforcing effect (see figure 6).The specific conductivity of this film is improving more than ten times than respective masses material more than 600 ℃, and therefore, it has potential using value in fields such as fuel cells.Embodiment 2. (ZrO
2)
0.92(Y
2O
3)
0.08Film
Accurately pipette Yttrium trinitrate and zirconium oxychloride solution, making its ratio in final oxide compound is required ZrO
2: Y
2O
3It is 0.92: 0.08, add the water of calculated amount, thorough mixing reaction 1h under induction stirring, add polyoxyethylene glycol then, making its content in finally being coated with stain liquid is 60mg/ml, after PEG dissolves fully, add dehydrated alcohol to required water alcohol than being 1: 6, abundant again stirring reaction 1h, gained colloidal sol filters with double-deck quantitative paper at last.Be rotated coating in ultra-clean chamber, rotating speed is 4000rpm/min, and the time is 15 seconds.Transfer to immediately in about 110 ℃ baking oven through the film that is coated with stain, dried by the fire 15 minutes.Be transferred to after from baking oven, taking out in 400 ℃ the low temperature diffusion stove, feeding under an amount of oxygen atmosphere presintering 20 minutes.Film is through repeating to be coated with the operation of stain, oven dry and presintering, until 25 layers.Feeding under an amount of oxygen atmosphere at last, 950 ℃ are carried out sintering to film.The gained film has the characteristics of surfacing, leakless, free of pinholes, uniform particles densification.Its thickness is 0.5 μ m.Nanocrystalline phase is pure fluorite structure cube phase (see figure 2), and the particulate mean sizes is 55nm (seeing Fig. 4 b).Embodiment 3. (ZrO
2)
0.92(Sc
2O
3)
0.04(YO
2)
0.04Film
Accurately pipette Scium trinitrate, Yttrium trinitrate and zirconium oxychloride solution, making its ratio in final oxide compound is required ZrO
2: Sc
2O
3: Y
2O
3It is 0.92: 0.04: 0.04, add the water of calculated amount, thorough mixing reaction 1h under induction stirring, add an amount of polyoxyethylene glycol then, making its content in finally being coated with stain liquid is 80mg/ml, after PEG dissolves fully, add dehydrated alcohol to required water alcohol than being 1: 7, abundant again stirring reaction 1h, gained colloidal sol filters with double-deck quantitative paper at last.Be rotated coating in ultra-clean chamber, rotating speed is 5000rpm/min, and the time is 8 seconds.Transfer to immediately in about 110 ℃ baking oven through the film that is coated with stain, dried by the fire 30 minutes.Be transferred to after from baking oven, taking out in 350 ℃ the low temperature diffusion stove, feeding under an amount of oxygen atmosphere presintering 20 minutes.Film is through repeating to be coated with the operation of stain, oven dry and presintering, until 20 layers.Feeding under an amount of oxygen atmosphere at last, 850 ℃ are carried out sintering to film.The gained film has the characteristics of surfacing, leakless, free of pinholes, uniform particles densification.Its thickness is 0.4 μ m.Nanocrystalline phase is pure fluorite structure cube phase, and the particulate mean sizes is 57nm.Embodiment 4. (ZrO
2)
0.82(RE
2O
3)
0.08(Al
2O
3)
0.10Film
Accurately pipette aluminum nitrate, Scium trinitrate and zirconium oxychloride solution, making its ratio in final oxide compound is required ZrO
2: Sc
2O
3: Al
2O
3It is 0.82: 0.08: 0.10, add the water of calculated amount, thorough mixing reaction 1h under induction stirring, add an amount of polyoxyethylene glycol then, making its content in finally being coated with stain liquid is 30mg/ml, after PEG dissolves fully, add dehydrated alcohol to required water alcohol than being 1: 5, abundant again stirring reaction 1h, gained colloidal sol filters with double-deck quantitative paper at last.Be rotated coating in ultra-clean chamber, rotating speed is 4500rpm/min, and the time is 20 seconds.Transfer to immediately in about 110 ℃ baking oven through the film that is coated with stain, dried by the fire 20 minutes.Be transferred to after from baking oven, taking out in 450 ℃ the low temperature diffusion stove, feeding under an amount of oxygen atmosphere presintering 20 minutes.Film is through repeating to be coated with the operation of stain, oven dry and presintering, until 30 layers.Feeding under an amount of oxygen atmosphere at last, 750 ℃ are carried out sintering to film.The gained film has the characteristics of surfacing, leakless, free of pinholes, uniform particles densification.Its thickness is 0.6 μ m.Nanocrystalline phase is pure fluorite structure cube phase, and the particulate mean sizes is 47nm.Embodiment 5. (ZrO
2)
0.70(RE
2O
3)
0.125(TiO
2)
0.175Film
Accurately pipette titanous chloride, Scium trinitrate and zirconium oxychloride solution, making its ratio in final oxide compound is required TiO
2: Sc
2O
3: ZrO
2=0.175: 0.125: 0.70, add the water of calculated amount, thorough mixing reaction 1h under induction stirring, add an amount of polyoxyethylene glycol then, making its content in finally being coated with stain liquid is 50mg/ml, after PEG dissolves fully, add dehydrated alcohol to required water alcohol than being 1: 8, abundant again stirring reaction 1h, gained colloidal sol filters with double-deck quantitative paper at last.Be rotated coating in ultra-clean chamber, rotating speed is 4000rpm/min, and the time is 10 seconds.Transfer to immediately in about 110 ℃ baking oven through the film that is coated with stain, dried by the fire 20 minutes.Be transferred to after from baking oven, taking out in 400 ℃ the low temperature diffusion stove, feeding under an amount of oxygen atmosphere presintering 20 minutes.Film is through repeating to be coated with the operation of stain, oven dry and presintering, until 30 layers.Feeding under an amount of oxygen atmosphere at last, 950 ℃ are carried out sintering to film.The gained film thickness is 0.6 μ m, and nanocrystalline phase is pure cube phase, and the particulate mean sizes is 50nm.
Claims (11)
1. the preparation method of a nanometer crystal film of rare earth doped ZrO 2 solid electrolyte, it is characterized in that: with inorganic salt of rare earth and zirconium inorganic salt is raw material, the amount beguine of the two is decided according to prepared film, polyoxyethylene glycol is a membrane-forming agent, and ethanol/water mixed solvent is a dispersion agent, makes to be coated with stain liquid, on silicon single crystal or quartz substrate, pass through repeatedly to apply, the film of desired thickness can be made, after this film annealing, nanometer crystal film of rare earth doped ZrO 2 solid electrolyte can be got.
2. the preparation method of claim 1 record, it is characterized in that: described inorganic salt of rare earth comprises rare earth nitrate and rare earth chloride, rare earth element is scandium, yttrium, lanthanum, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
3. the preparation method of claim 1 record is characterized in that the zirconium inorganic salt comprise Zircosol ZN and basic zirconium chloride.
4. the preparation method of claim 1 record, the molecular weight that it is characterized in that used polyoxyethylene glycol is 10000-40000.
5. the preparation method of claim 1 record is characterized in that in the raw material of forming with inorganic salt of rare earth and zirconium inorganic salt, can also further add al inorganic salt or Ti-inorganic salt.
6. the preparation method of claim 1 record is characterized in that used al inorganic salt is aluminum nitrate or aluminum chloride, and used Ti-inorganic salt is titanous chloride.
7. the preparation method of claim 1 record, it is characterized in that the described stain liquid that is coated with consists of: water and alcoholic acid volume ratio are 1: 5-1: between 8, PEG concentration is between 20mg/ml-80mg/ml, and concentration of metal ions is between 0.05 mol/l～0.2 mol/L.
8. the preparation method of claim 1 record, it is characterized in that being coated with consisting of of stain liquid: water and alcoholic acid volume ratio are 1: 8, and PEG concentration equals 40mg/ml, and concentration of metal ions is 0.10 mol/l.
9. the preparation method of claim 1 record is characterized in that described rotation coated conditions is rotating speed 3000～5000 rpm, and rotational time is 5～25 seconds, and gel dries by the fire down at 110 ℃ must do glue in 10～30 minutes, and the decomposition temperature scope of dried glue is 350～800 ℃.
10. the preparation method of claim 1 record is characterized in that annealing temperature is 650～950 ℃.
11. the preparation method of claim 1 record is characterized in that consisting of of the nano-crystal film made by aforesaid method:
(ZrO
2)
1-x(RE
2O
3)
x，
Or (ZrO
2)
1-x-y(RE
2O
3)
x(Al
2O
3)
y,
Or (ZrO
2)
1-x-y(RE
2O
3)
x(TiO
2)
y,
Wherein:
(ZrO
2)
1-x(RE
2O
3)
xThe scope of middle x is 0.02～0.24, and RE can be two kinds of different rare earth elements;
(ZrO
2)
1-x-y(RE
2O
3)
x(Al
2O
3)
yIn, when x=0.08, the scope of y is 0.02～0.20;
(ZrO
2)
1-x-y(RE
2O
3)
x(TiO
2)
yIn, when x=0.12, the scope of y is 0.05～0.20.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011098414A CN1188545C (en) | 2001-03-20 | 2001-03-20 | Prepn. of nanometer crystal film of rare earth doped ZrO2 solid electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011098414A CN1188545C (en) | 2001-03-20 | 2001-03-20 | Prepn. of nanometer crystal film of rare earth doped ZrO2 solid electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN1323920A true CN1323920A (en) | 2001-11-28 |
| CN1188545C CN1188545C (en) | 2005-02-09 |
Family
ID=4658169
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|---|---|---|---|
| CNB011098414A Expired - Fee Related CN1188545C (en) | 2001-03-20 | 2001-03-20 | Prepn. of nanometer crystal film of rare earth doped ZrO2 solid electrolyte |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417598C (en) * | 2006-06-08 | 2008-09-10 | 中南大学 | Preparation method of stable zirconium oxide nanometer material doped with samarium oxide |
| CN100423346C (en) * | 2004-06-18 | 2008-10-01 | 中国科学院过程工程研究所 | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte |
| CN101696033B (en) * | 2009-10-23 | 2011-05-04 | 山东理工大学 | Preparation method for synthesizing sheeted zirconia by using hydrothermal method |
| CN101500943B (en) * | 2006-08-17 | 2012-07-18 | H.C.施塔克有限公司 | Zirconium oxide and method for the production thereof |
| CN104945962A (en) * | 2015-05-13 | 2015-09-30 | 上海交通大学 | Metal oxide protective film and preparation method thereof |
| CN108172613A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of zirconium base gate dielectric material with high-k crystalline phase with and preparation method thereof |
| CN113371756A (en) * | 2021-07-13 | 2021-09-10 | 河南工业大学 | La-Sc-ZrO2 nano-crystal material and preparation method thereof |
-
2001
- 2001-03-20 CN CNB011098414A patent/CN1188545C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100423346C (en) * | 2004-06-18 | 2008-10-01 | 中国科学院过程工程研究所 | Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte |
| CN100417598C (en) * | 2006-06-08 | 2008-09-10 | 中南大学 | Preparation method of stable zirconium oxide nanometer material doped with samarium oxide |
| CN101500943B (en) * | 2006-08-17 | 2012-07-18 | H.C.施塔克有限公司 | Zirconium oxide and method for the production thereof |
| CN101696033B (en) * | 2009-10-23 | 2011-05-04 | 山东理工大学 | Preparation method for synthesizing sheeted zirconia by using hydrothermal method |
| CN104945962A (en) * | 2015-05-13 | 2015-09-30 | 上海交通大学 | Metal oxide protective film and preparation method thereof |
| CN108172613A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of zirconium base gate dielectric material with high-k crystalline phase with and preparation method thereof |
| CN113371756A (en) * | 2021-07-13 | 2021-09-10 | 河南工业大学 | La-Sc-ZrO2 nano-crystal material and preparation method thereof |
| CN113371756B (en) * | 2021-07-13 | 2023-04-25 | 河南工业大学 | La-Sc-ZrO2 nano crystal material and preparation method thereof |
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