CN114335642A - Bismuth oxide sintering-assisted zirconium oxide-based electrolyte and preparation method and application thereof - Google Patents
Bismuth oxide sintering-assisted zirconium oxide-based electrolyte and preparation method and application thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 51
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000005245 sintering Methods 0.000 title claims abstract description 48
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 122
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 43
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 23
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 22
- 235000015110 jellies Nutrition 0.000 claims description 22
- 239000008274 jelly Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000003980 solgel method Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 238000000280 densification Methods 0.000 abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 9
- 229960001484 edetic acid Drugs 0.000 description 9
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 9
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 8
- 241000968352 Scandia <hydrozoan> Species 0.000 description 4
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 compound bismuth oxide Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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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
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Abstract
The invention provides a bismuth oxide sintering-assisted zirconium oxide-based electrolyte and a preparation method thereof. According to the invention, the bismuth oxide and scandium oxide composite is adopted to stabilize the zirconia electrolyte, so that the densification sintering temperature can be effectively reduced, and meanwhile, higher conductivity can be ensured.
Description
Technical Field
The invention relates to the technical field of fuel cells/electrolytic cells, in particular to a bismuth oxide sintering-assisted zirconium oxide-based electrolyte and a preparation method and application thereof.
Background
The zirconia-based electrolyte is the most widely applied electrolyte material in the Solid Oxide Fuel Cell (SOFC) and the electrolytic cell (SOEC) at present, wherein 10 mol% of scandia-stabilized zirconia has the highest ionic conductivity and excellent mechanical strength, but the scandium element has higher cost, and reducing the scandium content while not reducing the ionic conductivity is one of the problems to be solved; another major problem of zirconia-based electrolytes is that the sintering temperature during the preparation process is high, generally higher than 1500 ℃, and excessive sintering temperature is likely to cause excessive growth of crystal grains, and excessive sintering of the anode may be caused during the preparation of the anode-supported battery, in addition, excessive sintering temperature may increase the manufacturing cost of the battery.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a bismuth oxide sintering-assisted zirconium oxide-based electrolyte, and a preparation method and application thereof. The method is used for solving the problems of high scandium content and high sintering temperature of the existing scandium oxide stabilized zirconia electrolyte.
In a first aspect, the present invention provides a bismuth oxide-promoted zirconia-based electrolyte, the zirconia-based electrolyte comprising bismuth oxide.
As a specific embodiment of the present invention, the zirconia-based electrolyte has a chemical formula of (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–x(ii) a Wherein x is [0.01, 0.3]]Preferably, [0.05,0.15]。
As a specific embodiment of the invention, the bismuth oxide is subjected to nano-scale compounding with stable zirconia containing 6 mol% of scandium oxide.
In a second aspect, the present invention provides a method for preparing a bismuth oxide-fired zirconia-based electrolyte, which is to composite bismuth oxide with stabilized zirconia containing 6 mol% of scandia in a nano-scale.
As a specific embodiment of the invention, the weight ratio of the bismuth oxide to the stable zirconia containing 6 mol% of scandium oxide is (1-30): 70-99); preferably, the ratio is (5-15): (85-95).
The specific embodiment of the invention comprises the step of compounding bismuth oxide and stabilized zirconia containing 6 mol% of scandium oxide in a nanometer scale by adopting a sol-gel method.
The specific embodiment of the invention also comprises the step of compounding bismuth oxide and stabilized zirconia containing 6 mol% of scandium oxide in a nanometer scale by adopting a mechanical mixing method.
As a specific embodiment of the invention, the method adopts a sol-gel method to compound bismuth oxide and stabilized zirconia containing 6mol percent of scandium oxide in a nanometer scale, and further comprises the following steps:
s1: dissolving scandium oxide and bismuth oxide in nitric acid solution, heating to volatilize water to obtain jelly;
s2: drying the jelly obtained in the step S1 to form precursor powder;
s3: and (5) sintering the precursor obtained in the step (S2) at constant temperature, and performing ball milling and screening on the sintered powder to finally obtain the zirconia-based electrolyte powder.
In the step S1, the concentration of the nitric acid solution is 0.5-2 mol/L, and the heating temperature is 50-100 ℃; in the step S2, the drying temperature is 200-300 ℃; in the step S3, the sintering temperature is 400-800 ℃, the sintering time is 4-6 h, the ball milling is carried out for 10-24h, and the powder is sieved to be below 200 meshes.
In a third aspect, the use of a bismuth oxide-promoted zirconia-based electrolyte in a fuel cell/electrolyser.
As a specific embodiment of the present invention, a solid oxide fuel cell includes an anode, an electrolyte including a bismuth oxide-co-fired zirconium oxide-based electrolyte, and a cathode.
The above raw materials in the present invention may be prepared by themselves or may be obtained commercially, and the present invention is not particularly limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1. the bismuth oxide sintering aid with high conductivity is adopted, so that the electrolyte has proper conductivity and the sintering temperature can be effectively reduced.
2. According to the zirconia base prepared in the embodiment of the invention, the introduction of bismuth oxide with different proportions can improve the conductivity of the electrolyte to different degrees, and meanwhile, compared with a mechanical mixing method, the conductivity of the electrolyte is improved to a certain degree by adopting a sol-gel method.
3. Compared with the traditional mechanical mixing method, the sol-gel one-step synthesis method has the advantages of uniform synthesis, nanoscale compounding and the like, can reduce the scandium content, effectively reduce the densification sintering temperature, ensure higher conductivity, and has relatively simple synthesis process, economy and feasibility, thereby being a method with development prospect.
Drawings
FIG. 1 is an electron micrograph (5000 times) of the surface morphology of the zirconia-based electrolyte obtained in example 5 of the present invention;
fig. 2 is an electron micrograph (5000 times) of the surface morphology of the electrolyte obtained in comparative example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the embodiments of the present invention, the observation and test method used is a scanning electron microscope.
In each embodiment of the invention, the battery performance is tested by adopting an electrochemical workstation, and the measurement frequency range is 0.1 Hz-1 MHz.
In each embodiment of the invention, the conductivity is tested by adopting an electrochemical workstation, and a specific method adopts a four-endpoint method for testing.
In each example of the present invention, the zirconia-based electrolyte powder was pressed into a sheet shape in the following process: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, and sintering at 900 ℃ for 10 h.
In each example of the present invention, the relative density is a ratio (minus%) of an actual density to a theoretical density of the zirconia-based electrolyte prepared in the example, and a larger ratio indicates a higher degree of compactness.
Example 1
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving (x is 0.01) in a stoichiometric ratio in a 0.5mol/L nitric acid solution, heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h to obtain a compact and bright strip-shaped sample, and testing the conductivity and the relative density to obtain the conductivity of 0.51S/cm; the relative density was 80.1.
Example 2
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate and lemonCitric acid, ethylene diamine tetraacetic acid according to the target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving the stoichiometric ratio of (x is 0.05) in 1mol/L nitric acid solution, heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 0.75S/cm; the relative density was 83.2.
Example 3
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–x(x ═ 0.1) in a stoichiometric ratio in a 1.5mol/L nitric acid solution, scandium oxide and bismuth oxide in a molar ratio of 90: 10, heating to 90 ℃, stirring to gradually volatilize water to obtain jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 0.95S/cm; the relative density was 90.1.
Example 4
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving the mixture in a stoichiometric ratio of (x is 0.15) in a 2mol/L nitric acid solution, heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 1.03S/cm; the relative density was 92.3.
Example 5
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–x(x is 0.2) in a stoichiometric ratio in a 0.5mol/L nitric acid solution, wherein scandia and scandia are dissolvedThe molar ratio of bismuth is 80: 20, heating to 90 ℃, stirring to gradually volatilize water to obtain jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 1.37S/cm; the relative density was 96.8.
The zirconia-based electrolyte obtained in example 5 was observed under a scanning electron microscope, as shown in fig. 1.
Example 6
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving the mixture in a 1.6mol/L nitric acid solution according to the stoichiometric ratio of (x is 0.25), heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 1.25S/cm; the relative density was 95.3.
Example 7
The embodiment provides a method for preparing a bismuth oxide sintering-assisted zirconium oxide-based electrolyte by adopting a sol-gel method, which comprises the following specific details:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving the mixture in a 1.2mol/L nitric acid solution according to the stoichiometric ratio of (x is 0.3), heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 1.11S/cm; the relative density was 93.2.
Example 8
The embodiment provides a method for preparing a bismuth oxide-sintering-assisted zirconium oxide-based electrolyte by adopting a mechanical mixing method, which comprises the following specific details:
the raw material proportioning scheme of example 1 was followed except that the zirconia-based electrolyte was prepared by a mechanical ball milling mixing method.
The zirconia-based electrolyte powder obtained in example 8 was pressed into a sheet shape, subjected to conductivity and relative density tests, and found to have a conductivity of 0.46S/cm; the relative density was 79.3.
Example 9
The present comparative example provides a method for preparing a bismuth oxide-promoted zirconia-based electrolyte using a mechanical mixing process, the details of which are as follows:
the zirconia-based electrolyte was prepared according to the raw material proportioning protocol of example 6, except that the mechanical ball milling mixing method was used.
The zirconia-based electrolyte powder obtained in example 9 was pressed into a sheet shape, and subjected to conductivity and relative density tests to find that the conductivity was 1.13S/cm; the relative density was 94.1.
Comparative example 1
The comparative example provides a method for preparing a zirconia-based electrolyte by a sol-gel method, the specific details of which are as follows:
s1: zirconium oxynitrate, scandium nitrate, bismuth nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving the stoichiometric ratio of (x is 0.5) in 1mol/L nitric acid solution, heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 0.55S/cm; the relative density was 90.5.
Comparative example 2
This comparative example provides a method of preparing a zirconia-based electrolyte using a sol-gel process, the components of which do not contain bismuth oxide, with the following specific details:
s1: zirconium oxynitrate, scandium nitrate, citric acid and ethylenediamine tetraacetic acid are mixed according to a target product (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–xDissolving (ScSZB, x is 0) in a 1mol/L nitric acid solution, wherein bismuth oxide is not contained, heating to 90 ℃, and stirring to gradually volatilize water to obtain a jelly;
s2: drying the jelly obtained in the step S1 in an oven at 250 ℃ to form precursor powder;
s3: sintering the precursor obtained in the step S2 at the constant temperature of 500 ℃ for 5h, further ball-milling the sintered powder for 24h, and sieving the powder with a sieve of less than 200 meshes to obtain bismuth oxide composite scandium oxide stabilized zirconia-based electrolyte powder;
s4: the zirconia-based electrolyte powder obtained in step S3 was pressed into a sheet shape by the following procedure: weighing 1g of electrode powder, maintaining the pressure for 3min under the pressure of 14Mpa by using an oil press to obtain a strip-shaped blank, sintering at 900 ℃ for 10h, and then testing the conductivity and the relative density to obtain the conductivity of 0.48S/cm; the relative density was 75.5.
The zirconia-based electrolyte obtained in comparative example 2 was observed under a scanning electron microscope as shown in fig. 2.
The test data lists for examples 1-9 and comparative examples 1-2 are compared, as shown in tables 1 and 2:
TABLE 1 measurement of conductivity and relative Density of zirconia-based electrolytes obtained in examples 1 to 9 and comparative examples 1 to 2
As can be seen from table 1, the zirconia-based electrolytes prepared by the sol-gel method in examples 1 and 6 are compared with the zirconia-based electrolytes prepared by the mechanical mixing method in examples 8 and 9, and as can be seen from the data in tables 1 and 2, the zirconia-based electrolyte powders synthesized by the sol-gel one-step process are more effective than the mechanical ball-milling mixing.
Comparative example 1 when the ratio of stabilized zirconia containing 6 mol% scandia to bismuth oxide was 1:1, the conductivity data was poor; comparative example 2 is prior art, contains no bismuth oxide and has poor conductivity data; compared with examples 1-9, the content of bismuth oxide is preferably 15-30 mol%, and the conductivity is most preferable when the content of bismuth oxide is 20 mol%.
Fig. 1 and 2 are photographs of the zirconia-based electrolytes obtained in example 5 and comparative example 2, respectively, observed under a scanning electron microscope, wherein the bismuth oxide content of example 5 is 20 mol%, and the comparative example contains no bismuth oxide; as is apparent from comparison of fig. 1 and 2, the zirconia-based electrolyte obtained in example 5 has a uniform texture and a density significantly higher than that of the zirconia-based electrolyte obtained in comparative example 2.
In conclusion, the bismuth oxide-assisted zirconia-based electrolyte disclosed by the invention can effectively reduce the densification sintering temperature and ensure higher conductivity by adopting the bismuth oxide composite scandium oxide stabilized zirconia electrolyte.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A bismuth oxide-promoted zirconia-based electrolyte, wherein the zirconia-based electrolyte comprises bismuth oxide.
2. The zirconia-based electrolyte of claim 1, wherein the zirconia-based electrolyte has a chemical formula of (Sc)2O3)0.06(Bi2O3)x(ZrO2)0.94–x；
Wherein, x takes the value of [0.01, 0.3], preferably [0.05,0.15 ].
3. The zirconia-based electrolyte according to claim 1 or 2, characterized by being obtained by nano-scale compounding of bismuth oxide with stabilized zirconia containing 6 mol% of scandium oxide.
4. A method for producing a bismuth oxide-fired zirconia-based electrolyte according to any one of claims 1 to 3, characterized in that bismuth oxide is nano-scale composited with stabilized zirconia containing 6 mol% of scandium oxide.
5. The method according to claim 4, wherein the molar ratio of bismuth oxide to stabilized zirconia containing 6 mol% of scandium oxide is (1-30): (70-99); preferably, the ratio is (5-15): (85-95).
6. The method according to claim 4 or 5, comprising nano-scale complexing bismuth oxide with stabilized zirconia containing 6 mol% of scandium oxide by a sol-gel method.
7. The method of claim 4, further comprising nano-scale complexing bismuth oxide with stabilized zirconia containing 6 mol% scandium oxide using a mechanical mixing method.
8. The preparation method according to claim 6, wherein the nano-scale compounding of bismuth oxide and stabilized zirconia containing 6 mol% of scandium oxide is performed by a sol-gel method, and comprises the following steps:
s1: dissolving scandium oxide and bismuth oxide in a nitric acid solution, and heating to remove water to obtain a jelly;
s2: drying the jelly obtained in the step S1 to obtain precursor powder;
s3: sintering the precursor powder obtained in the step S2, and ball-milling and screening the sintered powder to finally obtain the zirconia-based electrolyte powder.
9. The preparation method according to claim 8, wherein in the step S1, the concentration of the nitric acid solution is 0.5-2 mol/L, and/or the heating temperature is 50-100 ℃; and/or
In the step S2, the drying temperature is 200-300 ℃; and/or
In the step S3, the sintering temperature is 400-800 ℃, and/or the sintering time is 4-6 h, and/or the ball milling is carried out for 10-24h, and/or the sieving is carried out to below 200 meshes.
10. Use of a bismuth oxide-promoted zirconium oxide-based electrolyte according to claims 1 to 3 and/or a bismuth oxide-promoted zirconium oxide-based electrolyte prepared by the preparation method according to claims 4 to 9 in fuel cells/electrolysis cells.
11. A solid oxide fuel cell comprising an anode, an electrolyte and a cathode, wherein the electrolyte comprises the zirconia-based electrolyte according to any one of claims 1 to 3 and/or the zirconia-based electrolyte prepared by the preparation method according to any one of claims 4 to 9.
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