CN1661835A - Method for preparing anode of fuel cell in oxide of solid electrolyte - Google Patents
Method for preparing anode of fuel cell in oxide of solid electrolyte Download PDFInfo
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- CN1661835A CN1661835A CN2004100135819A CN200410013581A CN1661835A CN 1661835 A CN1661835 A CN 1661835A CN 2004100135819 A CN2004100135819 A CN 2004100135819A CN 200410013581 A CN200410013581 A CN 200410013581A CN 1661835 A CN1661835 A CN 1661835A
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- China
- Prior art keywords
- anode
- sintering
- hours
- ethyl alcohol
- absolute ethyl
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The method includes following steps: torrefying La2O3 for 12 hours under high temperature in order to remove impurity; after obtaining suitable proportioning of doping CeO2 by using different quantity of La2O3, grinding the admixture with absolute ethyl alcohol being added to; tabletting powder obtained by tablet machine and sintering the tablets under high temperature for 18 hours so as to obtain substance of barrier layer between electrolyte and anode; mixing the said substance of barrier layer and NiO according to certain proportion, and grinding the admixture with absolute ethyl alcohol being added to; then, sintering the admixture for two hours under high temperature so as to obtain anode substance. Features are: simple technique, easy of control, low cost. Advantages of the anode are: suitable for voiding ratio of anode, high conductivity, good chemical compatibility to electrolyte and thermal stability.
Description
(1) technical field:
The present invention proposes a kind of anode preparation method of solid electrolyte oxide fuel cell, specifically, be the barrier layer that on electrolyte, applies one deck blocking anode and the harmful chemical reaction of electrolyte generation, on the electrolyte barrier matrix, apply anode material then.
(2) background technology:
Fuel cell is the electrochemical energy conversion device that chemical energy is converted into electric energy.Poly-different as energy storage device with conventional power source plumbic acid, cadmium nickel, ni-mh, lithium ion and lithium, fuel cell has comparativity as a kind of electrochemical power generator with various generation technologies on function.In the conventional art, usually with the zirconia (YSZ) of stabilized with yttrium oxide as electrolyte, in order to obtain reasonable energy density, battery is all down work about 1000 ℃ generally, just because only under this temperature electrolyte YSZ possess desirable conductivity (greater than 0.1Scm
-1), 800 ℃ of following conductivity only are 1/4th under 1000 ℃.So high working temperature brings a series of in material, sealing and structural problem for solid electrolyte oxide fuel cell (SOFC), select difficulty etc. as thermal expansion matching between diffusion of the surface chemistry between sintering, electrolyte and the electrode of electrode and the material and bipolar material, these problems have seriously restricted the industrialized development of SOFC.Particularly development trend and the research focus of flat SOFC of SOFC is the research of warm SOFC in actively developing now, thereby solves the too high and a series of problems brought of working temperature.The key that addresses this problem is the warm conductivity of solid electrolyte down in being to improve, and one of approach is the novel solid electrolyte that (≤800 ℃) have high conductance under the temperature in adopting.Perovskite oxide material LaGaO 3 based solid electrolyte (LSGM) just gets more and more people's extensive concerning once proposition.
The prior art close with the present invention has the anode of the multiphase metal ceramics (Ni-LSGM) of selection Ni and LSGM as LSGM, but Ni can spread to LSGM under the high temperature, with the cenotype LaNiO of LSGM reaction generation
3High-insulation is an anode with Ni-LSGM, LaCo (Sr) O
3For the loss of the main power of test battery of negative electrode from anode polarization.Another kind of technology transfer Sm
2O
3The CeO that mixes
2(SDC), because it is the highest (0.0945Scm of rare metal oxide intermediate ion conductivity
-1), but in the multiphase metal ceramics system of SDC and LSGM, the generation that also responds between SDC and the LSGM, La
2O
3Can be from LSGM to Ce
1-xLa
xO
2-x/2Diffusion influences battery performance.
(3) summary of the invention:
One of main points of the present invention are to have applied the barrier layer that one deck can greatly improve battery performance between electrolyte and anode.With La
2O
3The CeO that mixes
2(LDC) as the barrier layer, can stop La from LSGM to CeO
2Diffusion, stop Ni adverse reaction to take place simultaneously to LSGM diffusion, stop mechanism stopping for macroscopic property; Two of main points are that prepared anode is a three-diemsnional electrode, and the zone of cell reaction is the phase reaction district.This is because adopted rare earth oxide CeO
2As the raw material of anode preparation, CeO
2As a kind of mixed ion conductor, reaction interface is not the two-dimentional interface that the electrolyte of normal conditions contacts with anode in the time of battery operated, but is deep into the three phase region of anode interior.
The present invention realizes according to the following steps:
1. preliminary treatment: with La
2O
3Baking is burnt 12 hours to remove impurity under 1000 ℃;
2. batch mixing: use La
2O
3Doped Ce O
2After obtaining suitable proportioning with mol ratio 20: 80 to 50: 50, add absolute ethyl alcohol and fully grind;
3. compressing tablet: the powder of batch mixing gained is pressed into circular test piece under 26MPa with tablet press machine;
4. barrier layer sintering: test piece was obtained barrier substance in 18 hours at 1450 ℃ of sintering;
5. anode sintering: add absolute ethyl alcohol after barrier substance and NiO mixed to 60: 40 by mass ratio 30: 70 and grind, obtained anode material in 2 hours at 1250 ℃ of sintering then.
Major advantage of the present invention has been to adopt the barrier layer effectively to stop harmful chemical reaction between the interface from the thermodynamics, prepared anode voidage is suitable, conductivity is high, with electrolyte good chemical compatibility and thermal stability are arranged, can greatly improve the chemical property and the useful life of battery, and cost is lower, technology is simple, easily control.
(4) embodiment:
Embodiment 1:
With La
2O
3Baking is burnt 12 hours to remove impurity, then with La under 1000 ℃
2O
3And CeO
2Mix at 20: 80 with mol ratio, adding absolute ethyl alcohol behind the mixing fully grinds, with tablet press machine under 26MPa with the circular test piece of the powder compaction of gained, the barrier substance that obtained between electrolyte and the anode in 18 hours at 1450 ℃ of sintering then, after again barrier substance and NiO being pressed 30: 70 mixed of mass ratio, add absolute ethyl alcohol and grind, obtained anode material in 2 hours at 1250 ℃ of following sintering then.Prepared anode porosity is 46%, and conductivity is 971Scm
-1, at 550mA/cm
2Current density under, the anode polarization value is 98mV.
Embodiment 2:
With La
2O
3Baking is burnt 12 hours to remove impurity, then with La under 1000 ℃
2O
3And CeO
2Mix at 30: 70 with mol ratio, adding absolute ethyl alcohol behind the mixing fully grinds, with tablet press machine under 26MPa with the circular test piece of the powder compaction of gained, the barrier substance that obtained between electrolyte and the anode in 18 hours at 1450 ℃ of sintering then, after again barrier substance and NiO being pressed 40: 60 mixed of mass ratio, add absolute ethyl alcohol and grind, obtained anode material in 2 hours at 1250 ℃ of following sintering then.Prepared anode porosity is 44%, and conductivity is 923Scm
-1, at 550mA/cm
2Current density under, the anode polarization value is 109mV.
Embodiment 3:
With La
2O
3Baking is burnt 12 hours to remove impurity, then with La under 1000 ℃
2O
3And CeO
2Mix at 40: 60 with mol ratio, adding absolute ethyl alcohol behind the mixing fully grinds, with tablet press machine under 26MPa with the circular test piece of the powder compaction of gained, the barrier substance that obtained between electrolyte and the anode in 18 hours at 1450 ℃ of sintering then, after again barrier substance and NiO being pressed 50: 50 mixed of mass ratio, add absolute ethyl alcohol and grind, obtained anode material in 2 hours at 1250 ℃ of following sintering then.Prepared anode porosity is 35%, and conductivity is 872Scm
-1, at 550mA/cm
2Current density under, the anode polarization value is 126mV.
Embodiment 4:
With La
2O
3Baking is burnt 12 hours to remove impurity, then with La under 1000 ℃
2O
3And CeO
2Mix at 50: 50 with mol ratio, adding absolute ethyl alcohol behind the mixing fully grinds, with tablet press machine under 26MPa with the circular test piece of the powder compaction of gained, the barrier substance that obtained between electrolyte and the anode in 18 hours at 1450 ℃ of sintering then, after again barrier substance and NiO being pressed 60: 40 mixed of mass ratio, add absolute ethyl alcohol and grind, obtained anode material in 2 hours at 1250 ℃ of following sintering then.Prepared anode porosity is 28%, and conductivity is 803Scm
-1, at 550mA/cm
2Current density under, the anode polarization value is 154mV.
Claims (1)
1, a kind of preparation method of solid electrolyte anode of oxide fuel cell is characterized in that: realize according to the following steps:
(1) preliminary treatment: with La
2O
3Baking is burnt 12 hours to remove impurity under 1000 ℃;
(2) batch mixing: use La
2O
3Doped Ce O
2After obtaining suitable proportioning with mol ratio 20: 80 to 50: 50, add absolute ethyl alcohol and fully grind;
(3) compressing tablet: the powder of batch mixing gained is pressed into circular test piece under 26MPa with tablet press machine;
(4) barrier layer sintering: test piece was obtained barrier substance in 18 hours at 1450 ℃ of sintering;
(5) anode sintering: add absolute ethyl alcohol after barrier substance and NiO mixed to 60: 40 by mass ratio 30: 70 and grind, obtained anode material in 2 hours at 1250 ℃ of sintering then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2004100135819A CN1661835A (en) | 2004-02-25 | 2004-02-25 | Method for preparing anode of fuel cell in oxide of solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2004100135819A CN1661835A (en) | 2004-02-25 | 2004-02-25 | Method for preparing anode of fuel cell in oxide of solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1661835A true CN1661835A (en) | 2005-08-31 |
Family
ID=35011001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004100135819A Pending CN1661835A (en) | 2004-02-25 | 2004-02-25 | Method for preparing anode of fuel cell in oxide of solid electrolyte |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106537679A (en) * | 2014-07-31 | 2017-03-22 | 富士胶片株式会社 | All-solid secondary battery, and method for manufacturing inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for batteries, and all-solid secondary battery |
| CN107223289A (en) * | 2015-02-06 | 2017-09-29 | 赛瑞斯知识产权有限公司 | The method for forming electrolyte |
-
2004
- 2004-02-25 CN CN2004100135819A patent/CN1661835A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106537679A (en) * | 2014-07-31 | 2017-03-22 | 富士胶片株式会社 | All-solid secondary battery, and method for manufacturing inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for batteries, and all-solid secondary battery |
| CN106537679B (en) * | 2014-07-31 | 2019-01-15 | 富士胶片株式会社 | All solid state secondary battery and its manufacturing method, inorganic solid electrolyte particle, solid electrolyte composition, battery electrode sheet |
| US10763542B2 (en) | 2014-07-31 | 2020-09-01 | Fujifilm Corporation | All solid-state secondary battery, inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for battery, and method for manufacturing all solid-state secondary battery |
| US11817548B2 (en) | 2014-07-31 | 2023-11-14 | Fujifilm Corporation | All solid-state secondary battery, inorganic solid electrolyte particles, solid electrolyte composition, electrode sheet for battery, and method for manufacturing all solid-state secondary battery |
| CN107223289A (en) * | 2015-02-06 | 2017-09-29 | 赛瑞斯知识产权有限公司 | The method for forming electrolyte |
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