CN100534906C - Method for synthesizing middle and low temperature oxygen ion conductor material - Google Patents

Method for synthesizing middle and low temperature oxygen ion conductor material Download PDF

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CN100534906C
CN100534906C CNB2007100518557A CN200710051855A CN100534906C CN 100534906 C CN100534906 C CN 100534906C CN B2007100518557 A CNB2007100518557 A CN B2007100518557A CN 200710051855 A CN200710051855 A CN 200710051855A CN 100534906 C CN100534906 C CN 100534906C
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conductor material
precursor solution
ionic conductor
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synthetic method
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CN101054195A (en
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张枫
徐庆
黄端平
陈文�
刘韩星
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Wuhan University of Technology WUT
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Abstract

The present invention provides a method for synthesizing the low temperature oxyanion conductor material with a Aurivillus structure of the Bi2Mex-yMe'x+yV1-xo5.35-delta system. The complexing reaction of bismuth nitrate and ethylene diamine tetraacetic acid is carried out in the deionized water according to the stoichiometric ratio of synthetic product, and then citric acid, nitrate of copper or cobalt, or carbonate of cobalt, and ammonia metatungstate and ammonia molybdate are added therein, then the clarifying and transparent solution of precursor is obtained after agitating; and the solution of precursor is heated, concentrated, expanded and coked to form the fluffy primary fine material which is heated to create the ultramicro composite powder with a size of 100~200 nm. The present invention has a simple technology, a short reaction time, fine and uniform particle of synthetic product, and can be used for an oxygen pump used in a middle and low temperature range of 300~600 DEG C, an electrochemical sensor, and an oxygen separation membrane, and has a broad application prospect.

Description

The synthetic method of cryogenic oxygen ionic conductor material in a kind of
Technical field
The present invention relates to the solid state ionic conductor field, particularly relate to a kind of synthetic Bi with Aurivillus structure 2Me X-yMe ' X+yV 1-xO 5.35-δ(Me=Cu or Co, Me '=W or Mo, x=0.1～0.2, y=0.02～0.2, δBe nonstoichiometry oxygen) synthetic method of cryogenic oxygen ionic conductor material in the system.
Background technology
Bi 2VO 5.5Be the novel middle cryogenic oxygen ionic conductor material that development in recent years is got up, this material is the Aurivillius structure, has by [Bi 2O 2] 2+Layer and [VO 3.5 0.5] 2-Layer (represents the oxygen room) is alternately arranged and the laminate structure of formation.By [VO 6] there is a large amount of oxygen rooms in the octahedra altogether vanadium oxygen perovskite-like layer that drift angle connects, thereby on the direction that is parallel to vanadium oxygen perovskite-like layer, produce high oxygen ionic conductivity.At Bi 2VO 5.5Fusing point (870 ℃) below, Bi 2VO 5.5Phase transformation with a series of complexity exists monocline α phase (temperature＜430 ℃), quadrature β phase (430 ℃～570 ℃) and cubic γ (temperature＞570 ℃) mutually respectively.Wherein, high temperature γ-Bi 2VO 5.5The oxide ion conduction performance the most excellent.Adopt other metal ion (as cupric ion, cobalt ion etc.) to replace Bi 2VO 5.5In part V ion, form Bi 2Me xV 1-xO 5.35-δSosoloid can at room temperature obtain the γ phase of high conductivity, and its oxide ion conduction rate reaches 10 in 300～600 ℃ middle low temperature range -3～10 -1Scm -1Level, this makes Bi 2Me xV 1-xO 5.35-δSystem has purposes widely at aspects such as oxygen pump, electrochemical sensor, oxygen separation membranes.Nearest studies show that, adopts two kinds of different metal ions to Bi 2VO 5.5Middle partly V ion carries out compound replacement, can further improve the oxide ion conduction performance of material.
At present, mainly adopt conventional solid-phase synthesis to prepare cryogenic oxygen ionic conductor material in this class, its main processes is: press stoichiometric ratio with Bi 2O 3, V 2O 5And other metal oxide mixing back ball milling, carry out repeatedly pre-burning at 650～800 ℃ then, (see J.Yan until the solid phase synthesis product that obtains single Aurivillus structure, M.Greenblatt, Solid StateIonics, 1995,81:225 and J.R.Dygas, M.Malys, F.Krok, W.Wrobel, A.Kozanecka and I.Abrahams, Solid State Ionics, 2005,178:2085).For cryogenic oxygen ionic conductor material in this class, usually need long-time (tens hours to tens hours) repeatedly, solid phase synthesis process repeatedly, could obtain to have the synthetic product of single Aurivillus structure, this just all brings difficulty to its research and application.Therefore, need to explore novel, the effective synthetic method of cryogenic oxygen ionic conductor material in this class.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of technology simple, easy synthetic Bi with Aurivillus structure 2Me X-yMe ' X+yV 1-xO 5.35-δThe method of cryogenic oxygen ionic conductor material in the system, and the thing phase purity height of synthetic product.
The technical scheme that the present invention solves its technical problem employing is: adopt the Bi that comprises the steps the synthetic a kind of Aurivillus of having structure 2Me X-yMe ' yV 1-xO 5.35-δCryogenic oxygen ionic conductor material in the system, in the molecular formula, Me=Cu or Co, Me '=W or Mo, x=0.1～0.2, y=0.02～0.2, δBe nonstoichiometry oxygen.
Complexing: the nitrate of bismuth or carbonate and ethylenediamine tetraacetic acid (EDTA) are carried out the aqueous solution that complexing obtains clear in deionized water.During complexing, the mol ratio of Bi ion and ethylenediamine tetraacetic acid (EDTA) is 1: 0.5～2, preferred 1: 1.2～2.
(2) preparation of precursor solution: in the resulting aqueous solution, add citric acid and the nitrate of copper or cobalt or the carbonate of cobalt, add ammonium meta-vanadate then, and ammonium metawolframate or ammonium molybdate; After heating under 30～60 ℃ of temperature and stirring 1～4 hour, obtain the precursor solution of clear.Resulting precursor solution, wherein the mol ratio of citric acid and each metal ion species total amount is 1～4: 1, the pH value of this solution is 7～10.
(3) preparation of primary products: precursor solution is heated, make it take place to concentrate, expansion, coking change, and forms fluffy elementary powder.When precursor solution was heated, its processing condition were: 150～350 ℃ of Heating temperatures, 0.5～10 hour heat-up time.
(4) preparation of sintetics: in retort furnace, elementary powder is heat-treated, obtain having the ultra tiny synthetic powder of single Aurivillus structure.When in retort furnace elementary powder being heat-treated, its processing condition are: 450～600 ℃ of thermal treatment temps, 0.5～2 hour time.
The invention has the beneficial effects as follows: synthesis technique is simple, and synthesis temperature is low, generated time is short, and building-up process is easy to control, favorable repeatability.Confirm that through X-ray diffraction (XRD) test synthetic product has single Aurivillus structure, is cubic γ phase.Confirm that through field emission scanning electron microscope (FESEM) test the particle of synthetic product is tiny, even again, granular size is 100～200nm.Adopt present method synthetic powder can obtain fine and close ceramic bar product in 0.5～4 hour at 550～700 ℃ of following sintering.With the oxide ion conduction performance of alternating-current impedance spectrometry test ceramics sample, confirm that the oxygen ionic conductivity of ceramics sample under 300 ℃ reaches 10 -2Scm -1Level, the oxygen ionic conductivity under 600 ℃ reaches 10 -1Scm -1Level.Present method synthetic product can be used in aspects such as the oxygen pump that uses, electrochemical sensor, oxygen separation membrane in 300～600 ℃ middle low temperature range, be with a wide range of applications.
Description of drawings
Fig. 1 is the Bi of embodiment 1 2Cu 0.05W 0.05V 0.9O 5.35-δThe XRD figure spectrum of superfine powder.
Fig. 2 is the Bi of embodiment 1 2Cu 0.05W 0.05V 0.9O 5.35-δThe FESEM photo of superfine powder.
Fig. 3 is for adopting the Bi of embodiment 1 2Cu 0.05W 0.05V 0.9O 5.35-δThe SEM photo of the prepared ceramics sample of superfine powder.
Fig. 4 is for adopting the Bi of embodiment 1 2Cu 0.05W 0.05V 0.9O 5.35-δThe Arrenhius relation curve of the oxygen ionic conductivity of the prepared ceramics sample of superfine powder.
Fig. 1 explanation: in the XRD figure of synthetic product the position of each diffraction peak and relative intensity all with γ-Bi 2VO 5.5Standard JCPDS card (44-0358) consistent, show that synthetic product has single AurivillIus structure, be cubic γ phase.
Fig. 2 explanation: the particle of synthetic powder is approximately spherical, no tangible agglomeration between particle, and grain graininess is even, and grain graininess mainly is distributed in 100～200nm scope.
Fig. 3 illustrates: adopt the ceramics sample intercrystalline combination of synthetic powder preparation tight, the microstructure densification.
Fig. 4 explanation: adopt the oxygen ionic conductivity of alternating-current impedance spectrometry test ceramics sample in 200-600 ℃ of temperature range, to the 1000/T mapping, obtain the Arrenhius relation curve of the oxygen ionic conductivity of ceramics sample according to log (σ T).The oxygen ionic conductivity of ceramics sample under 300 ℃ reaches 1.8 * 10 -2Scm -1, the oxygen ionic conductivity under 600 ℃ reaches 1.4 * 10 -1Scm -1
Embodiment
The invention provides a kind of Bi of the Aurivillus of having structure 2Mc X-yMe ' yV 1-xO 5.35-δThe synthetic method of cryogenic oxygen ionic conductor material in the system, its step that adopts comprise the preparation of complexing, precursor solution, the preparation of primary products, the preparation of sintetics.
The invention will be further described below in conjunction with embodiment, but do not limit the present invention.
Embodiment 1:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 1.2 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, add proper amount of deionized water, obtain the aqueous solution of clear after the stirring;
(2) preparation of precursor solution: press Bi 2Cu 0.05W 0.05V 0.9O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, nitric hydrate copper Cu (NO 3) 33H 2O and ammonium metawolframate, in the mol ratio of citric acid and each metal ion species total amount is that 3: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, and obtain the precursor solution of clear after stirring 2 hours under 40 ℃, the pH value of regulating precursor solution with ammoniacal liquor is 8;
(3) preparation of primary products: 300 ℃ of down heating 1 hour, precursor solution engenders variations such as concentrated, expansion, coking in heat-processed, forms fluffy elementary powder with precursor solution;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 500 ℃ and be incubated 1 hour, can obtain the synthetic powder of deep yellow.
Embodiment 2:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 1 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, are stirred to the aqueous solution that obtains clear after the adding proper amount of deionized water;
(2) preparation of precursor solution: press Bi 2Co 0.08W 0.02V 0.9O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, nitric hydrate cobalt Co (NO 3) 36H 2O and ammonium metawolframate, in the mol ratio of citric acid and each metal ion species total amount is that 2.5: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, at 50 ℃ of precursor solutions that obtain clear after stirring 1 hour down, the pH value of regulating precursor solution with ammoniacal liquor is 9;
(3) preparation of primary products: precursor solution is put into baking oven, and regulating oven temperature is 150 ℃, and precursor solution engenders variations such as concentrated, expansion, coking in 10 hours heat-processed, forms fluffy elementary powder;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 550 ℃ and be incubated 1.5 hours, can obtain the synthetic powder of brown.
Embodiment 3:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 2 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, are stirred to the aqueous solution that obtains clear after the adding proper amount of deionized water;
(2) preparation of precursor solution: press Bi 2Cu 0.02Mo 0.08V 0.9O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, nitric hydrate cobalt Cu (NO 3) 33H 2O and ammonium molybdate, in the mol ratio of citric acid and each metal ion species total amount is that 1.5: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, at 50 ℃ of precursor solutions that obtain clear after stirring 4 hours down, the pH value of regulating precursor solution with ammoniacal liquor is 10;
(2) preparation of primary products: 300 ℃ of down heating 1 hour, precursor solution engenders variations such as concentrated, expansion, coking in the heat-processed, forms fluffy elementary powder with precursor solution;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 600 ℃ and be incubated 2 hours, can obtain the xanchromatic synthetic powder.
Embodiment 4:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 1 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, are stirred to the aqueous solution that obtains clear after the adding proper amount of deionized water;
(2) preparation of precursor solution: press Bi 2Co 0.05Mo 0.05V 0.9O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, nitric hydrate cobalt Co (NO 3) 36H 2O and ammonium molybdate, in the mol ratio of citric acid and each metal ion species total amount is that 2: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, at 60 ℃ of precursor solutions that obtain clear after stirring 1 hour down, the pH value of regulating precursor solution with ammoniacal liquor is 8;
(3) preparation of primary products: 250 ℃ of down heating 3 hours, precursor solution engenders variations such as concentrated, expansion, coking in the heat-processed, forms fluffy elementary powder with precursor solution;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 500 ℃ and be incubated 1 hour, can obtain the synthetic powder of brown.
Embodiment 5:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 0.5 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, are stirred to the aqueous solution that obtains clear after the adding proper amount of deionized water;
(2) preparation of precursor solution: press Bi 2Co 0.1V 0.9O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, cobaltous carbonate CoCO 3In the mol ratio of citric acid and each metal ion species total amount is that 1: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, at 30 ℃ of precursor solutions that obtain clear after stirring 0.5 hour down, the pH value of regulating precursor solution with ammoniacal liquor is 7;
(3) preparation of primary products: precursor solution is put into baking oven, and regulating oven temperature is 150 ℃, and precursor solution engenders variations such as concentrated, expansion, coking in 10 hours heat-processed, forms fluffy elementary powder;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 450 ℃ and be incubated 0.5 hour, can obtain the synthetic powder of brown.
Embodiment 6:
(1) complexing: press Bi 3+With the mol ratio of ethylenediamine tetraacetic acid (EDTA) be 1: 0.5 ratio, with nitric hydrate bismuth Bi (NO 3) 35H 2O and ethylenediamine tetraacetic acid (EDTA) place beaker, are stirred to the aqueous solution that obtains clear after the adding proper amount of deionized water;
(2) preparation of precursor solution: press Bi 2Cu 0.2V 0.8O 5.35-δStoichiometric ratio take by weighing a certain amount of ammonium meta-vanadate NH 4VO 3, copper carbonate CoCO 3In the mol ratio of citric acid and each metal ion species total amount is that 4: 1 ratio adds citric acid, add in the previous step in the resulting aqueous solution, at 30 ℃ of precursor solutions that obtain clear after stirring 0.5 hour down, the pH value of regulating precursor solution with ammoniacal liquor is 7;
(3) preparation of primary products: precursor solution is put into baking oven, and regulating oven temperature is 350 ℃, and precursor solution engenders variations such as concentrated, expansion, coking in 0.5 hour heat-processed, forms fluffy elementary powder;
(4) preparation of sintetics: be placed on elementary powder in the crucible and send in the retort furnace, in air atmosphere, be heated to 500 ℃ and be incubated 0.5 hour, can obtain the synthetic powder of brown.
Resulting synthetic powder is analyzed after tested in the foregoing description, all can obtain similar result: have single Aurivillus structure with embodiment 1 (seeing Fig. 1 and Fig. 2), be cubic γ phase, it is spherical that powder granule is approximately, no tangible agglomeration between particle, grain graininess is even, and grain graininess mainly is distributed in 100～200nm scope.

Claims (5)

1. the synthetic method of cryogenic oxygen ionic conductor material in a kind is characterized in that a kind of Bi of the Aurivillus of having structure 2Me X-yMe ' yV 1-xO 5.35-δThe synthetic method of cryogenic oxygen ionic conductor material in the system, in the molecular formula, Me=Cu or Co, Me '=W or Mo, x=0.1～0.2, y=0.02～0.2, δ is a nonstoichiometry oxygen; Said method comprising the steps of:
(1) complexing: the nitrate of bismuth or carbonate and ethylenediamine tetraacetic acid (EDTA) are carried out complexing in deionized water, obtain the aqueous solution of clear;
(2) preparation of precursor solution: in the resulting aqueous solution, add citric acid and the nitrate of copper or cobalt or the carbonate of cobalt, add ammonium meta-vanadate then, and ammonium metawolframate or ammonium molybdate; After heating under 30～60 ℃ of temperature and stirring 1～4 hour, obtain the precursor solution of clear;
(3) preparation of primary products: precursor solution is heated, make it take place to concentrate, expansion, coking change, and forms fluffy elementary powder;
(4) preparation of sintetics: in retort furnace, elementary powder is heat-treated, obtain having the ultra tiny synthetic powder of single Aurivillus structure.
2. the synthetic method of cryogenic oxygen ionic conductor material in according to claim 1, it is characterized in that: when the nitrate of bismuth or carbonate and ethylenediamine tetraacetic acid (EDTA) carried out complexing, the mol ratio of Bi ion and ethylenediamine tetraacetic acid (EDTA) was 1: 1.2～2.
3. the synthetic method of cryogenic oxygen ionic conductor material in according to claim 1 is characterized in that: resulting precursor solution, and wherein the mol ratio of citric acid and each metal ion species total amount is 1～4: 1, the pH value of this solution is 7～10.
4. the synthetic method of cryogenic oxygen ionic conductor material in according to claim 1, when it is characterized in that precursor solution heated, its processing condition are: 150～350 ℃ of Heating temperatures, 0.5～10 hour heat-up time.
5. the synthetic method of cryogenic oxygen ionic conductor material in according to claim 1, when it is characterized in that in retort furnace elementary powder heat-treated, its processing condition are: 450～600 ℃ of thermal treatment temps, 0.5～2 hour time.
CNB2007100518557A 2007-04-12 2007-04-12 Method for synthesizing middle and low temperature oxygen ion conductor material Expired - Fee Related CN100534906C (en)

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CN107737536A (en) * 2017-09-30 2018-02-27 浙江海洋大学 A kind of dissolving method of bismuth salt
CN110227439B (en) * 2019-06-21 2020-07-03 河南大学 Preparation method of bismuth compound heterojunction composite nano material rich in oxygen vacancies
CN117049874A (en) * 2023-09-04 2023-11-14 桂林理工大学 Bismuth vanadate-based medium-low entropy oxygen ion conductor material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Bi2Me（0.1）V（0.9）O（5.5-δ）（Me=Co，Cu）体系的合成、结构与低温氧离子导电性能研究". 徐开群.《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》，第5期. 2006
"Bi2Me（0.1）V（0.9）O（5.5-δ）（Me=Co，Cu）体系的合成、结构与低温氧离子导电性能研究". 徐开群.《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》，第5期. 2006 *

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