CN102180508B - Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution - Google Patents

Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution Download PDF

Info

Publication number
CN102180508B
CN102180508B CN201110042024XA CN201110042024A CN102180508B CN 102180508 B CN102180508 B CN 102180508B CN 201110042024X A CN201110042024X A CN 201110042024XA CN 201110042024 A CN201110042024 A CN 201110042024A CN 102180508 B CN102180508 B CN 102180508B
Authority
CN
China
Prior art keywords
gdc
methyl ethyl
hydrate
preparation
ethyl diketone
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.)
Expired - Fee Related
Application number
CN201110042024XA
Other languages
Chinese (zh)
Other versions
CN102180508A (en
Inventor
沈春晖
邓凯
郭芷含
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.)
Wuhan University of Technology WUT
Original Assignee
Wuhan University of Technology WUT
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 Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN201110042024XA priority Critical patent/CN102180508B/en
Publication of CN102180508A publication Critical patent/CN102180508A/en
Application granted granted Critical
Publication of CN102180508B publication Critical patent/CN102180508B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a preparation method of a high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution, which can be applied to electrode support bodies of solid oxide fuel batteries. The preparation method of the high-crystallinity order mesoporous GDC solid solution is characterized by comprising the following steps of: (1) selecting raw materials; (2) preparing GDC precursor sol; (3) preparing a polymer solution; (4) pouring the GDC precursor sol into the polymer solution; (5) roasting; (6) when a mixed solution becomes sticky, removing a culture dish cover, and continuing a reaction for 40-60min to obtain a GDC/polyisoprene and polyethylene oxide segmented copolymer hybrid material; (7) calcining the material for 2-3h at 600-700 DEG C under an argon gas atmosphere; and (8) calcining carbon-containing GDC oxide solid solution powder for 2-3h at 400-500 DEG C under an air atmosphere to obtain the high-crystallinity order mesoporous GDC solid solution. The high-crystallinity order mesoporous GDC solid solution has the characteristics of high crystallinity, large specific surface area and regular channel structure.

Description

The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid
Technical field
The present invention relates to a kind of preparation method of order mesoporous gadolinium sesquioxide doped cerium oxide sosoloid.This order mesoporous sosoloid can be used for the electrode support of SOFC.
Background technology
Gadolinium sesquioxide doped cerium oxide (gadolinia doped ceria; GDC) under middle temperature (500～700 ℃) ionic conductivity than the traditional electrolyte oxidation of SOFC (SOFC) according to stable high 1～2 one magnitude of zirconium white (YSZ), be in the ideal, the low-temperature solid oxide fuel cell electrolyte.SOFC in, operation can be widened the range of choice of corresponding each element material greatly under the low temperature; The possibility that reduces to react between the cell device; To help reducing cost, improving the life-span; But in, operation can make the kinetic activity of electrode reduce under the low temperature, thereby have influence on the performance of battery.Therefore, must seek the electrode materials that is complementary with the gadolinium sesquioxide doped cerium oxide electrolyte.Recently, in order to improve the performance of electrode, the combined electrode of a kind of ion and electronics hybrid conductive becomes a main research focus.Ni/GDC composite anode materials for example, Ni has the catalyzed oxidation of fuel and the function of electronic conduction, and GDC is mainly as the supporter of Ni, and has the ionic conduction function.Same, lanthanum manganate (LSM)/GDC also is used as cathode material.The performance of these combined electrodes and gas three phase boundary (TPB) length have very big relation, and TPB length is grown and more had and utilizes the catalytic rate that improves electrode.The TPB of this length can reach through the GDC material that preparation has a uniform sequential pore structure.The pore passage structure of rule can improve dispersed and stable to catalyzer, thereby greatly improve catalytic activity.Therefore how to prepare have bigger serface, focus that regular pore canal structure, the high GDC hole material of stability become research.
Prepare order mesoporous crystallization GDC oxide solid solution and mainly adopt soft, hard template method; Soft template method adopts organic segmented copolymer to guide reagent as structure; Remove the GDC oxide solid solution that template obtains meso-hole structure through calcining in air; But this method is difficult to obtain high crystalline GDC oxide solid solution, because may cause mesoporous caving at the removing template that goes down of high-temperature very.Hard template method is that the GDC oxide precursor is penetrated in the hard template of ordered mesoporous silicon or charcoal, at high temperature removes template then, can obtain the mesoporous GDC oxide solid solution of high crystalline; And mesoporous being not easy caved in; But this method is time-consuming, and program is complicated, is difficult to control; It is also difficult to obtain the ideal hard template, and is difficult to let the GDC oxide precursor fill all holes.Therefore, it is imperative to explore a kind of preparation method of the order mesoporous GDC oxide solid solution of high crystallization of simple possible.
Summary of the invention
The preparation method who the purpose of this invention is to provide the order mesoporous gadolinium sesquioxide doped cerium oxide of a kind of high crystalline sosoloid, the percent crystallinity of the order mesoporous gadolinium sesquioxide doped cerium oxide sosoloid of this method preparation is high, specific surface area is big, and technology is simple.
To achieve these goals, the technical scheme that the present invention taked is: the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid is characterized in that it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5-2.5,
Methyl ethyl diketone gadolinium hydrate 0.35-0.45,
Methyl alcohol 20-30,
N, dinethylformamide 0.3-0.5,
THF 3.0-4.0,
Chloroform 5.0-6.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O), methyl alcohol and N, dinethylformamide (adds deionized water or does not add deionized water; When adding deionized water, the shared parts by weight of deionized water are 0.2-0.4), stirring at room 1-2 hour, obtain the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 65-70 ℃ of dissolving 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 65-70 ℃ of baking 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 40-60 minute (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2-3 hour (temperature rise rate is 20-25 ℃/minute) of 600-700 ℃ of calcining;
8) under air atmosphere, 400-500 ℃ of calcining carbonaceous GDC oxide solid solution powder 2-3 hour (temperature rise rate is 20-25 ℃/minute) obtains the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
Raw material in the said step 1) also comprises deionized water, and the shared parts by weight of deionized water are: 0.2-0.4; Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.
Water cut x=3-4 in the molecular formula of described methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate;
Described methyl alcohol, N, dinethylformamide, THF, chloroform are analytical pure, and purity is greater than 98wt%;
Described TR 301 and polyethylene oxide block copolymer number-average molecular weight are 50.5 * 10 3, MWD is 1.05, the weight percentage of polyoxyethylene segments is 15wt%.
Described TR 301 and polyethylene oxide block copolymer (polymer P I-PEO) be from Canadian Polymer Source, Inc. (Montreal Canada) directly buys, Http:// www.polymersource.com/
The present invention adopt have the active methyl ethyl diketone cerium of low in hydrolysis, the methyl ethyl diketone gadolinium is as the presoma of sol-gel; Adopt amphipathic TR 301 and polyethylene oxide block copolymer structure guiding reagent as the preparation of GDC oxide compound; Mode through self-assembly; The GDC oxide precursor selects swelling in hydrophilic polyoxyethylene segments; Remove polymer architecture guiding reagent through two step calcining procesies then; The firm decolorizing carbon that forms in the calcination process can support the wall of mesoporous GDC oxide solid solution effectively, has prevented mesoporous the caving in of GDC oxide solid solution when high temperature, therefore adopts present method can obtain the order mesoporous GDC oxide solid solution of high crystalline.
The present invention adopt have the active methyl ethyl diketone cerium of low in hydrolysis hydrate, methyl ethyl diketone gadolinium hydrate is as the presoma of GDC sol-gel; Adopt amphipathic TR 301 and polyethylene oxide block copolymer structure guiding reagent as the preparation of GDC oxide compound; Mode through self-assembly; The GDC oxide precursor selects swelling in hydrophilic polyoxyethylene segments, removes polymer architecture guiding reagent through two step calcining procesies then, in the template removal processes under the argon gas atmosphere; Polyoxyethylene segments is easy to decompose); But TR 301 is more stable, and it will be converted into firm decolorizing carbon, and this original position carbon can support the wall of mesoporous GDC oxide solid solution effectively; Prevent mesoporous the caving in of GDC oxide solid solution when high temperature, therefore adopt present method can obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
Compare with existing method, the present invention has following advantage:
1) the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation, with respect to soft template method, percent crystallinity is high, and has bigger serface, regular pore canal structure (being mesoporous orderly), stability height.
2) the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation, with respect to hard template method, it is simple to have technology, is easy to control.
The order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid of the present invention's preparation can be used for the electrode support of SOFC.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
THF 3.0,
Chloroform 5.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 1 hour obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 65 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 65 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 40 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 2:
The preparation method is with embodiment 1, only increases to the deionized water that do not add of embodiment 1 to add deionized water 0.315g.Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 3:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
Deionized water 0.315,
THF 4.0g,
Chloroform 6.0g,
TR 301 and polyethylene oxide block copolymer 0.5g,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl alcohol, N, dinethylformamide and deionized water, stirring at room 2 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 50 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 4:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
THF 4.0,
Chloroform 6.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 1.5 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 68 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 68 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 60 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2.5 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 2.5 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 5:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.554,
Methyl ethyl diketone gadolinium hydrate 0.355,
Methyl alcohol 25.37,
N, dinethylformamide 0.415,
THF 3.0,
Chloroform 5.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl alcohol and N, dinethylformamide (not adding deionized water), stirring at room 2 hours obtains stable GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained limpid polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 50 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 3 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 3 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 6:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5,
Methyl ethyl diketone gadolinium hydrate 0.35,
Methyl alcohol 20,
N, dinethylformamide 0.3,
Deionized water 0.2,
THF 3.0,
Chloroform 5.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=3), methyl alcohol and N, dinethylformamide adds deionized water, and stirring at room 1 hour obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 65 ℃ of dissolvings 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 65 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 40 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 2 hours (temperature rise rate is 20-25 ℃/minute) of 600 ℃ of calcinings;
8) under air atmosphere, 400 ℃ of calcining carbonaceous GDC oxide solid solution powders 2 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Embodiment 7:
The preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid, it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 2.5,
Methyl ethyl diketone gadolinium hydrate 0.45,
Methyl alcohol 30,
N, dinethylformamide 0.5,
Deionized water 0.4,
THF 4.0,
Chloroform 6.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate (Ce (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl ethyl diketone gadolinium hydrate (Gd (CH 3COCHCOCH 3) 3XH 2O, x=4), methyl alcohol and N, dinethylformamide adds deionized water, and stirring at room 2 hours obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 70 ℃ of dissolvings 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 70 ℃ of bakings 24 hours (gelation dehydration dealcoholysis) down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue 60 minutes (gelation reaction) of reaction, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 3 hours (temperature rise rate is 20-25 ℃/minute) of 700 ℃ of calcinings;
8) under air atmosphere, 500 ℃ of calcining carbonaceous GDC oxide solid solution powders 3 hours (temperature rise rate is 20-25 ℃/minute) obtain the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid.
The basic physicals test result such as the table 1 of the order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that obtains.
Table 1, the The performance test results of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid
Figure BDA0000047393570000081
Figure BDA0000047393570000091
The order mesoporous gadolinium sesquioxide doped cerium oxide of the high crystalline sosoloid that table 1 explanation embodiment of the invention 1-7 obtains has that percent crystallinity height, specific surface area are big, the characteristics of regular pore canal structure (be mesoporous in order).
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (like temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.

Claims (5)

1. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid is characterized in that it comprises the steps:
1) choosing of raw material:
By the shared parts by weight of each raw material be:
Methyl ethyl diketone cerium hydrate 1.5-2.5,
Methyl ethyl diketone gadolinium hydrate 0.35-0.45,
Methyl alcohol 20-30,
N, dinethylformamide 0.3-0.5,
THF 3.0-4.0,
Chloroform 5.0-6.0,
TR 301 and polyethylene oxide block copolymer 0.5,
Weighing methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol, N, dinethylformamide, THF, chloroform, TR 301 and polyethylene oxide block copolymer, subsequent use;
2) preparation of GDC precursor sol: in the there-necked flask of induction stirring is housed, add methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirring at room 1-2 hour, obtains the GDC precursor sol, stand for standby use;
3) preparation of polymers soln: THF and chloroform are mixed, obtain the mixed solvent of THF and chloroform; In the mixed solvent of THF and chloroform, add TR 301 and polyethylene oxide block copolymer, 65-70 ℃ of dissolving 1 hour, cool to room temperature obtained polymers soln then;
4) the GDC precursor sol is poured in the polymers soln, mixed at room temperature 1 hour obtains mixing solutions;
5) mixing solutions is poured in the glass culture dish, put into baking oven after covering the petridish lid, 65-70 ℃ of baking 24 hours down;
6) when mixing solutions becomes thickness, remove the petridish lid, continue reaction 40-60 minute, obtain GDC/ TR 301 and polyethylene oxide block copolymer hybrid material;
7) GDC/ TR 301 and polyethylene oxide block copolymer hybrid material are transferred to High Temperature Furnaces Heating Apparatus, under argon gas atmosphere,, obtain carbonaceous GDC oxide solid solution powder in 600-700 ℃ of calcining 2-3 hour;
8) under air atmosphere, calcined carbonaceous GDC oxide solid solution powder 2-3 hour, and obtained the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline sosoloid for 400-500 ℃.
2. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline according to claim 1 sosoloid, it is characterized in that: the raw material in the said step 1) also comprises deionized water, the shared parts by weight of deionized water are: 0.2-0.4; Deionized water is in step 2) in methyl ethyl diketone cerium hydrate, methyl ethyl diketone gadolinium hydrate, methyl alcohol and N, dinethylformamide stirs together.
3. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline according to claim 1 sosoloid is characterized in that: described methyl ethyl diketone cerium hydrate Ce (CH 3COCHCOCH 3) 3 xH 2O, methyl ethyl diketone gadolinium hydrate Gd (CH 3COCHCOCH 3) 3 xH 2Water cut in the molecular formula of O x=3-4.
4. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline according to claim 1 sosoloid is characterized in that: described methyl alcohol, N, and dinethylformamide, THF, chloroform are analytical pure, and purity is greater than 98wt%.
5. the preparation method of the order mesoporous gadolinium sesquioxide doped cerium oxide of high crystalline according to claim 1 sosoloid, it is characterized in that: described TR 301 and polyethylene oxide block copolymer number-average molecular weight are 50.5 * 10 3, MWD is 1.05, the weight percentage of polyoxyethylene segments is 15wt%.
CN201110042024XA 2011-02-21 2011-02-21 Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution Expired - Fee Related CN102180508B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110042024XA CN102180508B (en) 2011-02-21 2011-02-21 Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110042024XA CN102180508B (en) 2011-02-21 2011-02-21 Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution

Publications (2)

Publication Number Publication Date
CN102180508A CN102180508A (en) 2011-09-14
CN102180508B true CN102180508B (en) 2012-11-07

Family

ID=44566835

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110042024XA Expired - Fee Related CN102180508B (en) 2011-02-21 2011-02-21 Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution

Country Status (1)

Country Link
CN (1) CN102180508B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102623716B (en) * 2012-04-16 2013-12-25 哈尔滨工业大学 Preparation method of intermediate-temperature solid oxide fuel cell one-dimensional nano composite cathode
CN102807252B (en) * 2012-08-20 2014-07-30 上海应用技术学院 Mesoporous cerium zirconium solid solution composite oxide nano material and preparation method thereof
CN108448118B (en) * 2018-03-08 2019-04-09 湖南工学院 The preparation method of solid oxide electrode material with orderly 3D microchannel structure
CN112919522A (en) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 Cerium oxide material and preparation method and application thereof
CN111370740B (en) * 2020-03-11 2021-08-13 武汉工程大学 Preparation method and application of gadolinium oxide doped cerium oxide nano composite material
CN114735742A (en) * 2022-03-18 2022-07-12 清华大学 Doped nano oxide material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552344A (en) * 2009-05-05 2009-10-07 武汉理工大学 Method for preparing composite oxides mischcrystal jelly glue with gadolinium oxide adulterating cerium oxide
CN101719554A (en) * 2009-12-08 2010-06-02 中国科学院过程工程研究所 Test tube type mesothermal solid-oxide fuel cell
CN101962168A (en) * 2009-07-24 2011-02-02 中国矿业大学(北京) Method for preparing nano powder material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003084894A1 (en) * 2002-04-10 2003-10-16 Japan Science And Technology Agency Complex mixed conductor and its preparing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552344A (en) * 2009-05-05 2009-10-07 武汉理工大学 Method for preparing composite oxides mischcrystal jelly glue with gadolinium oxide adulterating cerium oxide
CN101962168A (en) * 2009-07-24 2011-02-02 中国矿业大学(北京) Method for preparing nano powder material
CN101719554A (en) * 2009-12-08 2010-06-02 中国科学院过程工程研究所 Test tube type mesothermal solid-oxide fuel cell

Also Published As

Publication number Publication date
CN102180508A (en) 2011-09-14

Similar Documents

Publication Publication Date Title
CN102180508B (en) Preparation method of high-crystallinity order mesoporous GDC (Gadolinia Doped Ceria) solid solution
CN103022446B (en) A kind of lithium ion battery silicon oxide/carbon negative material and preparation method thereof
CN100346510C (en) Surface modified positive pole material of lithium ion cell and preparation method thereof
CN101635348B (en) Tantalum-containing lithium ion battery cathode material lithium titanate preparation method
CN108199041B (en) Modified lithium iron phosphate material, preparation method and application
CN101609883B (en) Preparation method of nano-silver particle dispersed Li4Ti5O12 thin film lithium ion battery negative electrode
CN110247107B (en) Solid electrolyte, preparation method and application thereof
CN102683722A (en) Solid oxide fuel cell composite cathode and preparation method thereof
CN109817957B (en) Preparation method of asphalt-coated silicon-doped natural crystalline flake graphite negative electrode material
CN107017404A (en) A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide electrode material
CN103151508A (en) Lanthanum lithium titanate doped composite negative electrode material of lithium ion battery and preparation method thereof
CN107302083A (en) A kind of solid reaction process preparation method of nickel lithium manganate cathode material
CN105789606A (en) Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material
CN103151506A (en) Preparation method of nanoscale zirconium-doped lithium titanate material
CN101764204A (en) Preparation method of rear earth lanthanum doping type lithium manganate
CN105789607A (en) Preparation method of lithium titanate anode material doped with rare earth
CN109888256A (en) A kind of Si@SiOx@N doping TiO2-δMaterial and its preparation method and application
CN103441257B (en) A kind of preparation method of lithium titanate material
CN103928668A (en) Lithium ion battery and preparation method of anode material thereof
CN113078350A (en) Preparation method of rubidium-doped high-conductivity LLZTO/PEO composite solid electrolyte
CN105140540A (en) Lithium-air battery based on binder-free air electrode and preparation method of lithium-air battery
CN113060769A (en) Lithium cobaltate positive electrode material, preparation method thereof and lithium battery
CN103840132B (en) Ferrous carbonate/graphene composite material and its preparation method and application
CN103579599A (en) Preparation method of yttrium-containing lithium ion battery cathode material lithium titanate carbon-coated composite material
CN103219509B (en) Preparation method of lithium manganese oxide spinel positive material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20121107

Termination date: 20130221