CN112759392A - Multi-component co-doped cerium oxide-based solid electrolyte material and preparation method thereof - Google Patents
Multi-component co-doped cerium oxide-based solid electrolyte material and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 82
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 51
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 84
- 239000011259 mixed solution Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 58
- 239000000919 ceramic Substances 0.000 claims description 44
- 239000012528 membrane Substances 0.000 claims description 42
- 239000000446 fuel Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000000227 grinding Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 229910002852 Sm(NO3)3·6H2O Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 229910009253 Y(NO3)3 Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002001 electrolyte material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 2
- 229910052772 Samarium Inorganic materials 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 34
- 239000004372 Polyvinyl alcohol Substances 0.000 description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 description 24
- 229910000831 Steel Inorganic materials 0.000 description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021116 Sm(NO3)3.6H2O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910009246 Y(NO3)3.6H2O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
The invention discloses a multi-component co-doped cerium oxide-based solid electrolyte material, which has the following chemical formula: ce0.8YxGd0.04‑xSm0.16O1.9Wherein x is more than or equal to 0.02 and less than or equal to 0.035, Y, Gd and Sm are used as codopants for CeO2The solid electrolyte material is doped, so that the medium and low temperature ionic conductivity of the material can be greatly improved. The invention also discloses a preparation method of the multi-component co-doped cerium oxide-based solid electrolyte material, which adopts an ultrasonic microwave-assisted sol-gel method to prepare the solid electrolyte materialThe prepared powder material has the advantages of uniform component distribution, small particle size, uniform and compact crystal grains, capability of effectively improving the medium and low temperature ionic conductivity of the material, mild reaction conditions, easy size control, low sintering temperature, short reaction time and the like.
Description
Technical Field
The invention relates to the technical field of medium-low temperature fuel cell solid electrolytes, in particular to a multi-component co-doped cerium oxide-based solid electrolyte material and a preparation method thereof.
Background
Solid Oxide Fuel Cells (SOFC) are a new clean energy conversion device, which has the advantages of environmental friendliness, high energy conversion efficiency, and the like, and thus have attracted much attention from researchers. As it is well known that solid electrolytes are a core component of SOFCs, many solid electrolyte materials including doped zirconia, doped ceria and some new materials are currently studied and used. The traditional SOFC can have higher working efficiency only by working at the high temperature of more than 800 ℃, so that the cost of the cell is increased, and the popularization and application of the SOFC are limited. Therefore, the present research is mainly focused on developing a solid electrolyte material having high ionic conductivity in a medium-low temperature range.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a multi-component co-doped cerium oxide-based solid electrolyte material and a preparation method thereof.
The invention provides a multi-component co-doped cerium oxide-based solid electrolyte material, which has the following chemical formula: ce0.8YxGd0.04-xSm0.16O1.9Wherein x is more than or equal to 0.02 and less than or equal to 0.035.
Preferably, x is 0.03.
The preparation method of the multi-component co-doped cerium oxide-based solid electrolyte material comprises the following steps:
s1, weighing Gd (NO) according to the stoichiometric ratio3)3·6H2O、Sm(NO3)3·6H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving a proper amount of citric acid in deionized water to obtain a solution B;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to a set temperature under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction at the set temperature and the set pH under the combined action of the ultrasonic waves and the microwaves to obtain sol C;
and S4, cooling, aging and drying the sol C, grinding into powder, and heating and calcining to obtain the multi-component co-doped cerium oxide-based solid electrolyte material.
Preferably, the molar ratio of the citric acid to the metal ions in the mixed solution a is 1: (1.4-1.6).
Preferably, in the step S3, the temperature is set to be 20-80 ℃, the pH is set to be 6-8, and the reaction time is 3-5 h; in step S3, the ultrasonic power is 400-600W, and the microwave power is 600-1000W.
Preferably, in step S4, the specific method of heating and calcining is as follows: the temperature is firstly preserved for 20-40min at 30-150 ℃, then the temperature is raised to 350 ℃ for 60-80min, and then the temperature is raised to 800 ℃ for 150 ℃ for 200 min.
A preparation method of a solid electrolyte ceramic membrane of a medium-low temperature fuel cell comprises the following steps:
(1) grinding the multi-component co-doped cerium oxide-based solid electrolyte material prepared by the preparation method into powder, and adding a binder for granulation;
(2) tabletting the material obtained in the step (1) to obtain a flaky blank;
(3) and (3) sintering the flaky blank obtained in the step (2) at a high temperature to obtain the solid electrolyte ceramic membrane of the medium-low temperature fuel cell.
Preferably, in the step (2), the pressure of tabletting is 8-12 MPa; in the step (3), the sintering temperature is 1250-1350 ℃, and the sintering time is 2-4 h.
The invention has the following beneficial effects:
CeO2the base solid electrolyte material is an oxygen-deficient n-type semiconductor, has the advantages of low price, no toxicity, no pollution and the like, and is a green environment-friendly material. Pure CeO2The material cannot be used for a solid electrolyte. The present invention is to further improve CeO2The conductivity of the solid electrolyte material at medium and low temperature is realized by using Y, Gd and Sm as codopants to react with CeO2The solid electrolyte material is doped, so that oxygen ion vacancies are greatly increased, the electronic conductivity is reduced, and the low-temperature ionic conductivity can be greatly improved. Moreover, the solid electrolyte material is prepared by adopting the ultrasonic microwave-assisted sol-gel method, the prepared powder has uniform component distribution, smaller particle size and uniform and compact crystal grains, can effectively improve the medium and low temperature ionic conductivity of the material, and has the advantages of mild reaction conditions, easy size regulation, low sintering temperature, short reaction time and the like.
Drawings
FIG. 1 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9XRD characterization pattern of ceramic membrane.
FIG. 2 is Ce prepared in example 2 of the present invention0.8YxGd0.04-xSm0.16O1.9Scanning electron microscopy of ceramic membranes.
FIG. 3 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9Graph of conductivity of ceramic membranes at different temperatures.
FIG. 4 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9IR characterization of ceramic membranes。
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00012mol of Gd (NO)3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.00012mol Y(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material is disclosed, wherein x is 0.02.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain the Ce-based chemical formula0.8YxGd0.04- xSm0.16O1.9The ceramic membrane for the solid electrolyte of the medium-low temperature fuel cell, wherein x is 0.02.
Example 2
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00006mol of Gd (NO)3)3.6H2O、0.00018mol Y(NO3)3.6H2O、0.00096mol Sm(NO3)3.6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material is disclosed, wherein x is 0.03.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8YxGd0.04- xSm0.16O1.9The ceramic membrane for the solid electrolyte of the medium-low temperature fuel cell, wherein x is 0.03.
Example 3
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00003mol of Gd (NO)3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.00021mol Y(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material is disclosed, wherein x is 0.035.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8YxGd0.04- xSm0.16O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell, wherein x is 0.035.
Example 4
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00018mol of Gd (NO)3)3·6H2O、0.00006mol Y(NO3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9Of multicomponent co-dopingA cerium oxide-based solid electrolyte material, wherein x is 0.01.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8YxGd0.04- xSm0.16O1.9The ceramic membrane for a solid electrolyte of a medium-low temperature fuel cell, wherein x is 0.01.
Example 5
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00024mol of Gd (NO)3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material is disclosed, wherein x is 0.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8Gd0.04Sm0.16O1.9The ceramic membrane for the solid electrolyte of the medium-low temperature fuel cell, wherein x is 0.
Example 6
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00024mol Y (NO)3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min,cooling with the furnace to obtain the chemical formula Ce0.8YxGd0.04-xSm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material is disclosed, wherein x is 0.04.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8YxGd0.04- xSm0.16O1.9The ceramic membrane for a solid electrolyte of a medium-low temperature fuel cell, wherein x is 0.04.
Comparative example 1
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00012mol of Gd (NO)3)3·6H2O、0.00012mol Y(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, putting the powder into a muffle furnace, and heating at 100 DEG CKeeping the temperature for 30min, heating to 300 deg.C, keeping the temperature for 60min, heating to 750 deg.C, keeping the temperature for 180min, and furnace cooling to obtain Ce with chemical formula0.8Y0.02Gd0.02O1.9The multi-component co-doped cerium oxide-based solid electrolyte material.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8Y0.02Gd0.02O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
Comparative example 2
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00096mol of Sm (NO)3)3·6H2O、0.00012mol Y(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, putting the powder into a muffle furnace, and firstly, adding the powder into the muffle furnaceKeeping the temperature at 100 ℃ for 30min, then heating to 300 ℃ and keeping the temperature for 60min, then heating to 750 ℃ and keeping the temperature for 180min, and cooling along with the furnace to obtain the compound Ce with the chemical formula0.8Y0.02Sm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain a chemical formula Ce0.8Y0.02Sm0.16O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
Comparative example 3
Preparing a multi-component co-doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00012mol of Gd (NO)3)3·6H2O、0.00096mol Sm(NO3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, then grinding into powder, placing the powder in a muffle furnace,firstly preserving heat at 100 ℃ for 30min, then heating to 300 ℃ and preserving heat for 60min, then heating to 750 ℃ and preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8Gd0.02Sm0.16O1.9The multi-component co-doped cerium oxide-based solid electrolyte material.
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared multi-component co-doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain the Ce-based chemical formula0.8Gd0.02Sm0.16O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
Comparative example 4
Preparing a doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00012mol of Gd (NO)3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, firstly preserving the heat at 100 ℃ for 30min, then raising the temperature to 300 ℃ and preserving the heat for 60min, heating to 750 deg.C, holding for 180min, and furnace cooling to obtain Ce as chemical formula0.8Gd0.02O1.9The doped ceria-based solid electrolyte material of (1).
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain the Ce-based chemical formula0.8Gd0.02O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
Comparative example 5
Preparing a doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00096mol of Sm (NO)3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8Sm0.16O1.9The doped ceria-based solid electrolyte material of (1).
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain the Ce-based chemical formula0.8Sm0.16O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
Comparative example 6
Preparing a doped cerium oxide-based solid electrolyte material:
s1, weighing 0.00012mol Y (NO)3)3·6H2O、0.0048mol Ce(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving citric acid in deionized water to obtain a solution B, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: 1.5;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to 40 ℃ under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction for 4 hours under the combined action of the ultrasonic waves and the microwaves at the temperature of 40 ℃ and the pH of 7 to obtain sol C, wherein the ultrasonic power is 500W, and the microwave power is 800W;
s4, cooling, aging and drying the sol C, grinding the sol C into powder, placing the powder in a muffle furnace, preserving heat for 30min at 100 ℃, then raising the temperature to 300 ℃, preserving heat for 60min, raising the temperature to 750 ℃, preserving heat for 180min, and cooling along with the furnace to obtain the chemical formula Ce0.8Y0.02O1.9The doped ceria-based solid electrolyte material of (1).
The preparation method for preparing the solid electrolyte ceramic membrane of the medium-low temperature fuel cell comprises the following steps:
(1) grinding the prepared doped cerium oxide-based solid electrolyte material into powder, and adding a PVA (polyvinyl alcohol) binder for granulation;
(2) adding the material obtained in the step (1) into a steel die with the diameter of 14mm, and carrying out uniaxial extrusion tabletting under the pressure of 10MPa to obtain a flaky blank;
(3) sintering the flaky blank obtained in the step (2) at 1300 ℃ for 3h to obtain the Ce-based chemical formula0.8Y0.02O1.9The ceramic membrane of the solid electrolyte of the medium-low temperature fuel cell.
The ionic conductivity of the ceramic membrane is measured by using a domestic CHI660 electrochemical workstation and a GSL-1100X impedance meter. The test method is as follows: coating silver paste on two sides of a sample, drying in an oven at 400 ℃, keeping the temperature for 15min to remove organic matters, fixing platinum wires on the two sides as leads, wherein the heating rate is 10 ℃/min, and the voltage of an alternating current measurement signal is 0V. The prepared electrolyte ceramic sheet is dried in an air atmosphere at 400-800 ℃, and the Electrochemical Impedance (EIS) test frequency is as follows: low frequency 0.1HZ, high frequency 105HZ。
The ionic conductivities at 800 c of the ceramic membranes prepared in examples 1 to 6 and comparative examples 1 to 6 are shown in table 1.
TABLE 1 test results for ionic conductivity of ceramic membranes
FIG. 1 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9XRD characterization pattern of ceramic membrane, combined with XRD pattern of FIG. 1, which is compatible with cubic CeO2Compared with the standard card JCPDS No.81-0792, no diffraction peak is generated before 20 degrees, and the diffraction peaks are 28.460 degrees, 32.978 degrees, 47.321 degrees, 56.140 degrees, 58.878 degrees, 69.140 degrees, 76.381 degrees, 7 degreesA diffraction peak appears at 8.741 degrees and respectively corresponds to crystal faces of (111), (200), (220), (311), (222), (400), (331) and (420)), and the product is the cubic system CeO2The purity of the product is higher. The average grain size of the ceramic film was calculated to be 53nm according to the Scherrer formula.
FIG. 2 is Ce prepared in example 2 of the present invention0.8YxGd0.04-xSm0.16O1.9Scanning electron microscopy of ceramic membranes. In fig. 2, the magnifications of (a), (b), (c), and (d) are 3500, 2500, 1500, and 1000, respectively. As shown in fig. 2, the sample has uniform particle size and good compactness, and can clearly observe that the surface of the crystal grain is approximately spherical, the combination between the particles is tight, and the arrangement is regular, and it can be seen from the figure that the surface crystal grain grows well, and no air holes are found, which indicates that the ceramic membrane has good compactness, uniform distribution and relatively uniform and dense crystal grain size.
FIG. 3 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9Graph of conductivity of ceramic membranes at different temperatures. As can be seen from fig. 3, the conductivity generally increases with increasing temperature.
FIG. 4 is Ce prepared in the examples of the present invention0.8YxGd0.04-xSm0.16O1.9IR characterization of ceramic membranes. It can be seen that the main absorption peaks of the different ceramic membranes are from left to right at 632cm-1，840cm-1，1356cm-1，1566cm-1，1651cm-1，3155cm-1A distinct characteristic absorption peak appears.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. Multi-component co-doped cerium oxide-based solid electrolyteA material characterized in that the chemical formula of the electrolyte material is as follows: ce0.8YxGd0.04-xSm0.16O1.9Wherein x is more than or equal to 0.02 and less than or equal to 0.035.
2. The multi-component co-doped cerium oxide-based solid electrolyte material according to claim 1, wherein x is 0.03.
3. A method for producing the multi-component co-doped cerium oxide-based solid electrolyte material according to claim 1 or 2, comprising the steps of:
s1, weighing Gd (NO) according to the stoichiometric ratio3)3·6H2O、Sm(NO3)3·6H2O、Ce(NO3)3·6H2O、Y(NO3)3·6H2Dissolving the O in deionized water to obtain a mixed solution A;
s2, dissolving a proper amount of citric acid in deionized water to obtain a solution B;
s3, placing the mixed solution A and the solution B in an ultrasonic and microwave combined reaction system, starting an ultrasonic wave generating device and a microwave generating device, heating the mixed solution A and the solution B to a set temperature under the combined action of ultrasonic waves and microwaves, then dropwise adding the solution B into the mixed solution A, uniformly mixing, and carrying out heat preservation reaction at the set temperature and the set pH under the combined action of the ultrasonic waves and the microwaves to obtain sol C;
and S4, cooling, aging and drying the sol C, grinding into powder, and heating and calcining to obtain the multi-component co-doped cerium oxide-based solid electrolyte material.
4. The method for preparing the multi-component co-doped cerium oxide-based solid electrolyte material according to claim 3, wherein the molar ratio of the citric acid to the metal ions in the mixed solution A is 1: (1.4-1.6).
5. The preparation method of the multi-component co-doped cerium oxide-based solid electrolyte material according to claim 3 or 4, wherein in the step S3, the temperature is set to be 20-80 ℃, the pH is set to be 6-8, and the reaction time is 3-5 h; in step S3, the ultrasonic power is 400-600W, and the microwave power is 600-1000W.
6. The method for preparing the multi-component co-doped cerium oxide-based solid electrolyte material according to any one of claims 3 to 5, wherein in the step S4, the specific method of heating and calcining is as follows: the temperature is firstly preserved for 20-40min at 30-150 ℃, then the temperature is raised to 350 ℃ for 60-80min, and then the temperature is raised to 800 ℃ for 150 ℃ for 200 min.
7. A preparation method of a solid electrolyte ceramic membrane of a medium-low temperature fuel cell is characterized by comprising the following steps:
(1) grinding the multi-component co-doped cerium oxide-based solid electrolyte material prepared by the preparation method of any one of claims 3 to 6 into powder, and adding a binder for granulation;
(2) tabletting the material obtained in the step (1) to obtain a flaky blank;
(3) and (3) sintering the flaky blank obtained in the step (2) at a high temperature to obtain the solid electrolyte ceramic membrane of the medium-low temperature fuel cell.
8. The method for preparing a solid electrolyte ceramic membrane for a middle-low temperature fuel cell according to claim 7, wherein in the step (2), the pressure of the pressed sheet is 8 to 12 MPa; in the step (3), the sintering temperature is 1250-1350 ℃, and the sintering time is 2-4 h.
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