CN106602136A - Barium zirconate-based electrolyte material system and preparation method thereof - Google Patents
Barium zirconate-based electrolyte material system and preparation method thereof Download PDFInfo
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- CN106602136A CN106602136A CN201611201296.9A CN201611201296A CN106602136A CN 106602136 A CN106602136 A CN 106602136A CN 201611201296 A CN201611201296 A CN 201611201296A CN 106602136 A CN106602136 A CN 106602136A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention provides a barium zirconate-based electrolyte material system and a preparation method thereof, and belongs to the field of solid oxide fuel cells. The electrolyte material system is BaZr<0.8>Gd<0.2-x>Zn<x>O<3-delta>, wherein x is equal to 0, 0.02, 0.04 or 0.06; a proton conductor BaZrO<3> is selected as the electrolyte material system and trivalent cations Y<3+> are doped, so that the proton conductivity of the BaZrO<3> is improved. Through the addition of a ZnO sintering aid, the sintering capacity is improved and the sintering temperature of the electrolyte material is reduced, so that the prepared BaZr<0.8>Gd<0.2-x>Zn<x>O<3-delta> (x=0, 0.02, 0.04 or 0.06) has overall performance of sintering activity, conductivity, chemical stability and mechanical property. The barium zirconate-based electrolyte material system has the advantages that good chemical stability can be kept, the micro vickers hardness can reach 719.58MPa and the compressive strength can reach 29.68MPa.
Description
Technical field
The present invention relates to a kind of proton conductive type electrolyte new material system and preparation method, belong to solid oxide fuel
Field of batteries.
Background technology
SOFC (SOFC) is received due to the advantage such as its high energy conversion rate and low stain thing emission index
To extensive concern.Proton conductive type SOFC (H- can be divided into according to the difference of its electrolyte conductive ion
) and ionic conduction type SOFC (O-SOFC) SOFC.For in O-SOFC, mass transport process starts from negative electrode, oxygen
Gas Dissociative under cathode catalysis effect, and electronics is obtained, form oxonium ion O2-, through fine and close electricity under high keto sectional pressure effect
H generated and oxidation reaction with the fuel of anode in solution matter there is2O or CO2And electronics is discharged, and electronics forms current strap by external circuit
Dynamic load works；And in H-SOFC, mass transport process starts from anode, proton is captured to be formed by the electron cloud of Lattice Oxygen in fuelAnd electronics is discharged, the rotational transition between proton is by electrolyte lattice oxygen in the case where tolerance electromotive force drives reaches cathode side,
And with the oxonium ion for being enriched in cathode side react generation H2O.H-SOFC is low with conducting activation energy compared with O-SOFC,
The advantages such as fuel availability height.
Proton conductor electrolyte is mainly BaCeO3-BaZrO3Based on system, because it is in low temperature range internal ratio oxonium ion
The higher and lower Conductance activation energy of the ionic conductivity of conductor.BaCeO3Though base electrolyte is with high proton conductive,
When 500 DEG C, the electrical conductivity of BZCY has 9 × 10-3S/cm, but it is easy to CO2And H2O occurs, and the chemical stability of material is mutually on duty.
And BaZrO3Although base electrolyte material is to CO2And H2O has good inertia and reasonable crystal grain conductance, but sintering is lived
Property is poor, and 1700 DEG C of high temperature sintering causes crystal grain to be grown up rapidly, and grain boundary conductivities are extremely low.
The content of the invention
It is an object of the invention to provide a kind of barium zirconate base electrolyte material system and preparation method thereof, solves BaZrO3
Sintering temperature is high, the low problem of grain boundary resistance.
The object of the present invention is achieved like this：Select proton conductor BaZrO3As electrolyte material system, doping three
Valency cation Y3+, improve BaZrO3Proton conductivity, add ZnO sintering aids, increase its caking power, reduce electrolyte
Sintering temperature so that prepare BaZr0.8Gd0.2-xZnxO3-δ(x=0,0.02,0.04,0.06) obtain and there is sintering to live
The combination property of property, electrical conductivity, chemical stability and mechanical performance.
Preparation method step is：
1st, the electrolyte powder to be made of the invention is BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, root
Needed raw material is calculated according to the molal weight of every kind of element：C4H6BaO4、Zr(NO3)4·3H2O、Gd(NO3)3·6H2O, ZnO's
Quality；
2nd, oxide ZnO and zirconium compound Zr (NO is weighed3)4·3H2O adds 50-100ml distillations in a clean beaker
Water, then add 10-15ml nitric acid, heating is stirred to solution clarification；
3rd, raw material C is weighed4H6BaO4, Gd (NO3)3·6H2O, and chelating agent citric acid, ethylenediaminetetraacetic acid (EDTA)；Network
Mixture ratio is metal ion：Citric acid：EDTA=1：1：0.8；Four kinds of materials are all added after a upper beaker, plus 30-50ml
Ammonia, heating, stirring is until solution clarification；
4th, the settled solution for preparing is put in aluminium oxide ceramics pot and is heated, stirred to solution and become viscous, and play occurs
After the completion of strong spontaneous combustion reaction, collection to be cooled, this is initial powder, finally initial powder is put into into pre-burning in batch-type furnace
1100 DEG C of -3h, are obtained electrolyte powder.
Beneficial effect, as a result of such scheme, using the mode of Gd and Zn codopes, obtains sintering activity, chemistry
The proton type electrolyte material system BaZr of the excellent combination properties such as stability, electrical conductivity and mechanical performance0.8Gd0.2-xZnxO3-δ
Wherein x=0,0.02,0.04,0.06.1300 DEG C of Jing of sample difference after pre-burning pressed by powder molding, 1400 DEG C, 1500 DEG C of sintering
BaZr after 5h, after 1400 DEG C of sintering0.8Gd0.14Zn0.06O3-δRelative density up to 89.12%, SEM also provable this conclusion.
Sample Jing boiling water decocting in water 3 hours and 100%CO2After atmosphere processes 10h at 700 DEG C, good chemical stability is still kept.
BaZr0.8Gd0.14Zn0.06O3-δElectrical conductivity reaches 2.5 × 10 when 750 DEG C are found after electrochemical property test-3S/cm.This
Outward, hardness and intensity test, the BaZr after 1500 DEG C of sintering have been carried out0.8Gd0.16Zn0.04O3-δDimensional microstructure formula hardness can
Up to 719.58MPa, comprcssive strength is up to 29.68MPa.
Advantage：Good chemical stability can be kept, dimensional microstructure formula hardness is up to 719.58MPa, and comprcssive strength is reachable
29.68MPa。
Description of the drawings
Fig. 1 is embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δ, wherein x=0,0.02,0.04,0.06, XRD diffraction after pre-burning
Figure.
Fig. 2 is embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δ, wherein x=0,0.02,0.04,0.06, compressing rear burning
Relative density curve chart after knot 1300 DEG C of -5h, 1400 DEG C of -5h, 1500 DEG C of -5h.
Fig. 3 is embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, compressing rear sintering
The SEM shape appearance figures of 1400 DEG C of -5h.
Fig. 4 is embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, sample is through 100%
CO2 processes the XRD diffraction patterns after 10h.
Fig. 5 is embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, electrical conductivity with temperature
Variation relation figure.
Fig. 6 a are embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06 burns through different temperatures
Dimensional microstructure formula hardness number figure after knot.
Fig. 6 b are embodiment 1-4BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06 burns through different temperatures
Compression strength value figure after knot.
Specific embodiment
The present invention includes barium zirconate base electrolyte material system and the preparation method of barium zirconate base electrolyte material system.
Select proton conductor BaZrO3Used as electrolyte material system, adulterate Tricationic Y3+, improve BaZrO3Matter
Electron conductivity, adds ZnO sintering aids, increases its caking power, reduces the sintering temperature of electrolyte, so that preparing
BaZr0.8Gd0.2-xZnxO3-δ(x=0,0.02,0.04,0.06) obtain and have sintering activity, electrical conductivity, chemical stability and machine
The combination property of tool performance.
Described preparation method step is：
1st, the electrolyte powder to be made of the invention is BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, root
Needed raw material is calculated according to the molal weight of every kind of element：C4H6BaO4、Zr(NO3)4·3H2O、Gd(NO3)3·6H2O, ZnO's
Quality；
2nd, oxide ZnO and zirconium compound Zr (NO is weighed3)4·3H2O adds 50-100ml distillations in a clean beaker
Water, then add 10-15ml nitric acid, heating is stirred to solution clarification；
3rd, raw material C is weighed4H6BaO4, Gd (NO3)3·6H2O, and chelating agent citric acid, ethylenediaminetetraacetic acid (EDTA)；Network
Mixture ratio is metal ion：Citric acid：EDTA=1：1：0.8；Four kinds of materials are all added after a upper beaker, plus 30-50ml
Ammonia, heating, stirring is until solution clarification；
4th, the settled solution for preparing is put in aluminium oxide ceramics pot and is heated, stirred to solution and become viscous, and play occurs
After the completion of strong spontaneous combustion reaction, collection to be cooled, this is initial powder, finally initial powder is put into into pre-burning in batch-type furnace
1100 DEG C of -3h, are obtained electrolyte powder.
Embodiment 1.BaZr0.8Gd0.2-xZnxO3-δ(BZG) electrolyte is as x=0, according to the molal weight meter of every kind of element
The quality of needed raw material is calculated, after the completion of calculating, oxide ZnO and zirconium compound Zr (NO is weighed first3)4·3H2O is clean in one
In beaker, 50-100ml distilled water is added, then add 10-15ml nitric acid, heating is stirred to solution clarification；Then weigh
C4H6BaO4, Gd (NO3)3·6H2Four kinds of materials are added upper single firing by O, chelating agent citric acid and ethylenediaminetetraacetic acid (EDTA)
After cup, plus 30-50ml ammonia, heated and stirred is until solution is clarified；The settled solution for preparing is put in aluminium oxide ceramics pot
Heat and stir, until solution becomes viscous and occur violent spontaneous combustion reaction, collect after cooling, this is initial powder；Most
Afterwards initial powder is put into into 1100 DEG C of -3h of pre-burning in batch-type furnace, electrolyte powder is obtained.
Embodiment 2.BaZr0.8Gd0.2-xZnxO3-δ(BZG-0.02Zn) electrolyte is as x=0.02, according to every kind of element
Molal weight calculates the quality of needed raw material, after the completion of calculating, oxide ZnO and zirconium compound Zr (NO is weighed first3)4·
3H2O adds 50-100ml distilled water in a clean beaker, then adds 10-15ml nitric acid, and heating is stirred to solution clarification；So
After weigh C4H6BaO4, Gd (NO3)3·6H2O, chelating agent citric acid and ethylenediaminetetraacetic acid (EDTA), four kinds of materials are added
After a upper beaker, plus 30-50ml ammonia, heated and stirred is until solution is clarified；The settled solution for preparing is put into into aluminium oxide pottery
Heat in porcelain pot and stir, until solution becomes viscous and occur violent spontaneous combustion reaction, collect after cooling, this is initial powder
Body；Finally initial powder is put into into 1100 DEG C of -3h of pre-burning in batch-type furnace, electrolyte powder is obtained.
Embodiment 3.BaZr0.8Gd0.2-xZnxO3-δ(BZG-0.04Zn) electrolyte is as x=0.04, according to every kind of element
Molal weight calculates the quality of needed raw material, after the completion of calculating, oxide ZnO and zirconium compound Zr (NO is weighed first3)4·
3H2O adds 50-100ml distilled water in a clean beaker, then adds 10-15ml nitric acid, and heating is stirred to solution clarification；So
After weigh C4H6BaO4, Gd (NO3)3·6H2O, chelating agent citric acid and ethylenediaminetetraacetic acid (EDTA), four kinds of materials are added
After a upper beaker, plus 30-50ml ammonia, heated and stirred is until solution is clarified；The settled solution for preparing is put into into aluminium oxide pottery
Heat in porcelain pot and stir, until solution becomes viscous and occur violent spontaneous combustion reaction, collect after cooling, this is initial powder
Body；Finally initial powder is put into into 1100 DEG C of -3h of pre-burning in batch-type furnace, electrolyte powder is obtained.
Embodiment 4.BaZr0.8Gd0.2-xZnxO3-δ(BZG-0.06Zn) electrolyte is as x=0.06, according to every kind of element
Molal weight calculates the quality of needed raw material, after the completion of calculating, oxide ZnO and zirconium compound Zr (NO is weighed first3)4·
3H2O adds 50-100ml distilled water in a clean beaker, then adds 10-15ml nitric acid, and heating is stirred to solution clarification；So
After weigh C4H6BaO4, Gd (NO3)3·6H2O, chelating agent citric acid and ethylenediaminetetraacetic acid (EDTA), four kinds of materials are added
After a upper beaker, plus 30-50ml ammonia, heated and stirred is until solution is clarified；The settled solution for preparing is put into into aluminium oxide pottery
Heat in porcelain pot and stir, until solution becomes viscous and occur violent spontaneous combustion reaction, collect after cooling, this is initial powder
Body；Finally initial powder is put into into 1100 DEG C of -3h of pre-burning in batch-type furnace, electrolyte powder is obtained.
Claims (2)
1. a kind of barium zirconate base electrolyte material system, is characterized in that：Select proton conductor BaZrO3As electrolyte body
System, adulterate Tricationic Y3+, improve BaZrO3Proton conductivity, add ZnO sintering aids, increase its caking power, reduce
The sintering temperature of electrolyte, so that preparing BaZr0.8Gd0.2-xZnxO3-δ(x=0,0.02,0.04,0.06) are had
There is the combination property of sintering activity, electrical conductivity, chemical stability and mechanical performance.
2. a kind of preparation method of the barium zirconate base electrolyte material system described in claim 1, is characterized in that：Preparation method is walked
Suddenly it is：
(1), the electrolyte powder to be made of the invention is BaZr0.8Gd0.2-xZnxO3-δWherein x=0,0.02,0.04,0.06, according to
The molal weight of every kind of element calculates needed raw material：C4H6BaO4、Zr(NO3)4·3H2O、Gd(NO3)3·6H2The matter of O, ZnO
Amount；
(2) oxide ZnO and zirconium compound Zr (NO, is weighed3)4·3H2O adds 50-100ml distilled water in a clean beaker,
Again plus 10-15ml nitric acid, heating, stirs to solution clarification；
(3), raw material C is weighed4H6BaO4, Gd (NO3)3·6H2O, and chelating agent citric acid, ethylenediaminetetraacetic acid (EDTA)；Complexation
Agent ratio is metal ion：Citric acid：EDTA=1：1：0.8；Four kinds of materials are all added after a upper beaker, plus 30-50ml ammonia
Water, heating, stirring is until solution clarification；
(4), the settled solution for preparing is put in aluminium oxide ceramics pot and is heated, stirred to solution and become viscous, and occurred violent
Spontaneous combustion reaction after the completion of, collection to be cooled, this is initial powder, finally initial powder is put into into pre-burning 1100 in batch-type furnace
DEG C -3h, is obtained electrolyte powder.
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| CN201611201296.9A CN106602136A (en) | 2016-12-22 | 2016-12-22 | Barium zirconate-based electrolyte material system and preparation method thereof |
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| CN201611201296.9A CN106602136A (en) | 2016-12-22 | 2016-12-22 | Barium zirconate-based electrolyte material system and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242554A (en) * | 2018-01-10 | 2018-07-03 | 郑州大学 | A kind of barium cerate base electrolyte material and its preparation method and application |
| CN117895040A (en) * | 2024-03-15 | 2024-04-16 | 山东理工大学 | Proton conductor electrolyte material with high chemical stability and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467869A (en) * | 2002-06-06 | 2004-01-14 | ���µ�����ҵ��ʽ���� | Solid electrolyte fuel cell and manufacturing method thereof |
| CN103165930A (en) * | 2013-03-25 | 2013-06-19 | 南京工业大学 | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte |
| CN103531833A (en) * | 2013-10-22 | 2014-01-22 | 天津大学 | Proton conductor material in lithium/yttrium carbonate doped cerium barium zirconium complex phase structure |
| WO2016157566A1 (en) * | 2015-03-30 | 2016-10-06 | 住友電気工業株式会社 | Proton conductor, fuel-cell solid-electrolyte layer, cell structure, and fuel cell provided with same |
-
2016
- 2016-12-22 CN CN201611201296.9A patent/CN106602136A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467869A (en) * | 2002-06-06 | 2004-01-14 | ���µ�����ҵ��ʽ���� | Solid electrolyte fuel cell and manufacturing method thereof |
| CN103165930A (en) * | 2013-03-25 | 2013-06-19 | 南京工业大学 | Method for Improving Sintering Performance of Proton Conductor Solid Oxide Fuel Cell Electrolyte |
| CN103531833A (en) * | 2013-10-22 | 2014-01-22 | 天津大学 | Proton conductor material in lithium/yttrium carbonate doped cerium barium zirconium complex phase structure |
| WO2016157566A1 (en) * | 2015-03-30 | 2016-10-06 | 住友電気工業株式会社 | Proton conductor, fuel-cell solid-electrolyte layer, cell structure, and fuel cell provided with same |
Non-Patent Citations (3)
| Title |
|---|
| CHENG PENG 等: "BaZr0.8Y0.2O3−δ electrolyte with and without ZnO sintering aid: Preparation and characterization", 《SOLID STATE IONICS》 * |
| JUNFU BU 等: "Sintering behaviour of the protonic conductors BaZrxCe0.8-xLn0.2O3-δ(x=0.8,0.5,0.1;Ln=Y,Sm,Gd,Dy)during the solid-state", 《CERAMICS INTERNATIONAL》 * |
| 顾庆文等: "用于固体氧化物燃料电池的Zn掺杂BaZr0.7Pr0.1Y0.2O3–δ质子导体电解质的制备与性能", 《硅酸盐学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242554A (en) * | 2018-01-10 | 2018-07-03 | 郑州大学 | A kind of barium cerate base electrolyte material and its preparation method and application |
| CN108242554B (en) * | 2018-01-10 | 2020-07-17 | 郑州大学 | Barium cerate-based electrolyte material and preparation method and application thereof |
| CN117895040A (en) * | 2024-03-15 | 2024-04-16 | 山东理工大学 | Proton conductor electrolyte material with high chemical stability and preparation method thereof |
| CN117895040B (en) * | 2024-03-15 | 2024-06-04 | 山东理工大学 | Proton conductor electrolyte material with high chemical stability and preparation method thereof |
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Application publication date: 20170426 |