CN111584911B - Fe3O4-BCFN intermediate temperature composite solid electrolyte and preparation method thereof - Google Patents
Fe3O4-BCFN intermediate temperature composite solid electrolyte and preparation method thereof Download PDFInfo
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 206010021143 Hypoxia Diseases 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 39
- 239000010955 niobium Substances 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 27
- 239000011812 mixed powder Substances 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011240 wet gel Substances 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 159000000009 barium salts Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 31
- 239000004372 Polyvinyl alcohol Substances 0.000 description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000004913 activation Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000002001 electrolyte material Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- -1 oxygen ion Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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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
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- Y02E60/50—Fuel cells
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Abstract
The invention discloses Fe3O4-BCFN intermediate temperature composite solid electrolyte and preparation method thereof, wherein the electrolyte comprises Ba1.0Co0.7Fe0.2Nb0.1O3‑δAnd Fe3O4In which Fe3O4The content in the electrolyte is 5-15wt%, ba1.0Co0.7Fe0.2Nb0.1O3‑δHas a double perovskite structure, and delta is oxygen deficiency. Fe prepared by the invention3O4the-BCFN intermediate-temperature composite solid electrolyte has excellent thermal stability and electric conductivity within the temperature range of 400-800 ℃, and is an intermediate-temperature solid electrolyte material with prospect.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to Fe3O4-BCFN intermediate temperature composite solid electrolyte and its preparation method.
Background
Conventional solid electrolyte materials have been widely used in the high temperature field, but this limits the range of choices for electrolyte materials. In order to realize the commercial application and market expansion of the fuel cell, medium and low temperature solid electrolyte materials are developed, the material selection temperature of each component of the cell is reduced to be below 1000 ℃, the production cost is reduced, and the development trend of the electrolyte materials is realized.
The key factor for the wide commercial application of batteries is that the cathode material of the battery has not only excellent electrochemical properties but also good thermal stability under the continuous working conditions of the battery. Ba1-xCo0.7Fe0.2Ni0.1O3-δ、 BaZr0.1Ce0.7Y0.2O3-δThe electrolyte is a mesophilic solid electrolyte material which is researched more at present, but the conductivity of the electrolyte is general under mesophilic conditions, and the thermal stability is low. Therefore, in order to improve the fuel cell performance to a greater extent and reduce the electrode polarization caused by the temperature change, it is necessary to further study an intermediate-temperature solid electrolyte material for a fuel cell having good electrochemical performance and high thermal stability.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides Fe3O4-BCFN intermediate-temperature composite solid electrolyte and a preparation method thereof.
The invention provides Fe3O4-BCFN intermediate temperature composite solid electrolyte, the composition of the electrolyte comprises Ba1.0Co0.7Fe0.2Nb0.1O3-δAnd Fe3O4In which Fe3O4The content in the electrolyte is 5-15wt%, ba1.0Co0.7Fe0.2Nb0.1O3-δHas a double perovskite structure, and delta is oxygen deficiency.
Preferably, fe3O4The content in the electrolyte was 10wt%.
One kind of Fe3O4-a method for preparing a BCFN intermediate temperature composite solid electrolyte, comprising the following steps:
s1, mixing Fe3O4Powder and Ba having double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder, wherein Fe in the mixed powder3O4The content of the powder is 5-15wt%, preferably 10wt%;
s2, mixing the mixed powder with a binder, grinding uniformly, and performing compression molding to obtain a blank;
s3, preserving the temperature of the blank at 1050-1150 ℃ for 1.5-2.5h to obtain the product.
Preferably, said Ba having a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe preparation method of the powder comprises the following steps:
(1) Push Ba1.0Co0.7Fe0.2Nb0.1O3-δRespectively weighing barium salt, cobalt salt, ferric salt and niobium pentoxide according to the stoichiometric ratio, and dissolving the barium salt, the cobalt salt and the ferric salt in water to obtain a solution A;
(2) Dissolving the niobium pentoxide weighed in the step (1) in a nitric acid solution to obtain a solution B;
(3) After the solution A and the solution B are mixed, adding a proper amount of citric acid and glycol, and uniformly stirring to obtain a mixed solution;
(4) Adjusting the pH value of the mixed solution to 4-8, and then stirring and reacting at 70-85 ℃ to obtain wet gel;
(5) Drying the wet gel at 100-140 ℃ for 8-15h, and then preserving heat at 1150-1250 ℃ for 1.5-2.5h to obtain the gel.
Preferably, in the step (3), the molar amount of citric acid added is 1.4-1.6 times of the total molar amount of Ba, co, fe and Nb.
Preferably, in the step (3), the molar amount of the ethylene glycol added is 1.15 to 1.3 times of the molar amount of the citric acid.
Preferably, the barium salt is barium nitrate, the cobalt salt is cobalt nitrate, and the iron salt is ferric nitrate.
The invention has the following beneficial effects:
the invention prepares Ba with a double perovskite structure by a sol-gel self-combustion method1.0Co0.7Fe0.2Nb0.1O3-δ(BCFN)，And by appropriate proportions of Fe3O4Form Fe with good performance3O4The BCFN intermediate-temperature composite solid electrolyte has high ionic conductivity in a high-temperature stage, but has small ionic conductivity in a medium-temperature stage and a low-temperature stage due to the fact that the BCFN with the double perovskite structure has low ionic conductivity, and Fe3O4After the material, the conductivity can be greatly improved, which is because of Fe3O4The presence of low-priced Fe in the material2+、Fe3+Partial replacement of Nb with a similar ionic radius5+、Co3+Ions are generated, more oxygen ion vacancies are generated, the ion migration number and the conductivity are improved within a certain range of compounding, but too much compounding amount can cause the oxygen ion vacancies and the cations to form association, the ion transmission is hindered, and the conductivity is reduced; meanwhile, the sintering aid has the functions of reducing the sintering temperature, improving the sintering activity and increasing the thermal stability. Thus, the Fe of the present invention is compared to the undoped BCFN solid electrolyte3O4the-BCFN composite solid electrolyte can greatly improve the conductivity and the thermal stability within the temperature range of 400-800 ℃, and has good application prospect.
Drawings
Fig. 1 to 3 show XRD test results of samples of solid electrolytes prepared in example 3 and comparative examples 1 to 6.
FIG. 4 is a graph showing the results of conductivity tests on solid electrolyte samples of example 3, comparative examples 1 to 4 and comparative example 6
Fig. 5 is an activation energy test result of the solid electrolyte samples of example 3, comparative examples 1 to 4, and comparative example 6.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
Preparation of Ba having a double perovskite Structure1.0Co0.7Fe0.2Nb0.1O3-δPowder:
(1) Push Ba1.0Co0.7Fe0.2Nb0.1O3-δOf (2) is a stoichiometric ratioRespectively weighing barium nitrate, cobalt nitrate, ferric nitrate and niobium pentoxide, and dissolving the barium nitrate, the cobalt nitrate and the ferric nitrate in water to obtain a solution A;
(2) Dissolving the niobium pentoxide weighed in the step (1) in a nitric acid solution to obtain a solution B;
(3) Mixing the solution A and the solution B, adding citric acid which is 1.4 times of the total molar weight of Ba, co, fe and Nb and ethylene glycol which is 1.15 times of the molar weight of the citric acid, and uniformly stirring to obtain a mixed solution;
(4) Adjusting the pH value of the mixed solution to 4, and then stirring and reacting at 70 ℃ to obtain wet gel;
(5) Drying the wet gel at 100 deg.C for 8h, and keeping the temperature at 1150 deg.C for 1.5 h.
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing 5wt% of Fe3O4Powder and 95wt% of Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder;
s2, mixing the mixed powder with a PVA (polyvinyl alcohol) binder, grinding uniformly, and performing compression molding to obtain a blank;
s3, preserving the temperature of the blank at 1050 ℃ for 1.5h to obtain the product.
Example 2
Preparation of Ba having a double perovskite Structure1.0Co0.7Fe0.2Nb0.1O3-δPowder:
(1) Press Ba1.0Co0.7Fe0.2Nb0.1O3-δRespectively weighing barium nitrate, cobalt nitrate, ferric nitrate and niobium pentoxide according to the stoichiometric ratio, and dissolving the barium nitrate, the cobalt nitrate and the ferric nitrate in water to obtain a solution A;
(2) Dissolving the niobium pentoxide weighed in the step (1) in a nitric acid solution to obtain a solution B;
(3) Mixing the solution A and the solution B, adding citric acid which is 1.6 times of the total molar weight of Ba, co, fe and Nb and ethylene glycol which is 1.3 times of the molar weight of the citric acid, and uniformly stirring to obtain a mixed solution;
(4) Adjusting the pH value of the mixed solution to 8, and then stirring and reacting at 85 ℃ to obtain wet gel;
(5) Drying the wet gel at 140 deg.C for 15h, and keeping the temperature at 1250 deg.C for 2.5 h.
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing 15wt% of Fe3O4Powder and 85wt% of Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder;
s2, mixing the mixed powder with a PVA binder, uniformly grinding, and performing compression molding to obtain a blank;
s3, preserving the temperature of the blank at 1150 ℃ for 2.5h to obtain the product.
Example 3
Preparation of Ba having a double perovskite Structure1.0Co0.7Fe0.2Nb0.1O3-δPowder:
(1) Push Ba1.0Co0.7Fe0.2Nb0.1O3-δRespectively weighing barium nitrate, cobalt nitrate, ferric nitrate and niobium pentoxide according to the stoichiometric ratio, and dissolving the barium nitrate, the cobalt nitrate and the ferric nitrate in water to obtain a solution A;
(2) Dissolving the niobium pentoxide weighed in the step (1) in a nitric acid solution to obtain a solution B;
(3) Mixing the solution A and the solution B, adding citric acid which is 1.5 times of the total molar weight of Ba, co, fe and Nb and ethylene glycol which is 1.2 times of the molar weight of the citric acid, and uniformly stirring to obtain a mixed solution;
(4) Adjusting the pH value of the mixed solution to 6, and then stirring and reacting at 80 ℃ to obtain wet gel;
(5) Drying the wet gel at 110 deg.C for 12h, and keeping the temperature at 1200 deg.C for 2 h.
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing 10wt% of Fe3O4Powder and 90wt% of Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder;
s2, mixing the mixed powder with a PVA binder, uniformly grinding, and performing compression molding to obtain a blank;
and S3, preserving the temperature of the blank at 1100 ℃ for 2h to obtain the product.
Comparative example 1
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing Fe3O4Powder and Ba having double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder, wherein Fe is contained in the mixed powder3O4The content of the powder is 20wt%, and the powder has Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe powder was prepared as in example 3;
s2, mixing the mixed powder with a PVA (polyvinyl alcohol) binder, grinding uniformly, and performing compression molding to obtain a blank;
and S3, preserving the temperature of the blank at 1100 ℃ for 2h to obtain the product.
Comparative example 2
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing Fe3O4Powder and Ba with double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder, wherein Fe is contained in the mixed powder3O4The content of the powder is 30wt%, and the Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe powder was prepared as in example 3;
s2, mixing the mixed powder with a PVA (polyvinyl alcohol) binder, grinding uniformly, and performing compression molding to obtain a blank;
and S3, preserving the temperature of the blank at 1100 ℃ for 2h to obtain the product.
Comparative example 3
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing Fe3O4Powder and Ba having double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder, wherein Fe is contained in the mixed powder3O4The content of the powder is 40wt%, and the powder has Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe powder was prepared as in example 3;
s2, mixing the mixed powder with a PVA (polyvinyl alcohol) binder, grinding uniformly, and performing compression molding to obtain a blank;
s3, preserving the temperature of the blank at 1100 ℃ for 2 hours to obtain the finished product.
Comparative example 4
Preparation of Fe3O4-BCFN composite solid electrolyte:
s1, mixing Fe3O4Powder and Ba having double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder, wherein Fe is contained in the mixed powder3O4The content of the powder is 50wt%, and the Ba with a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe powder was prepared as in example 3;
s2, mixing the mixed powder with a PVA (polyvinyl alcohol) binder, grinding uniformly, and performing compression molding to obtain a blank;
and S3, preserving the temperature of the blank at 1100 ℃ for 2h to obtain the product.
Comparative example 5
Preparation of BCFN solid electrolyte:
s1, preparation of Ba having a double perovskite Structure according to the method of example 31.0Co0.7Fe0.2Nb0.1O3-δPowder;
s2, ba to be of double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δMixing the powder with a PVA binder, uniformly grinding, and performing compression molding to obtain a blank;
and S3, preserving the temperature of the blank at 1100 ℃ for 2h to obtain the product.
Comparative example 6
Preparation of BCFN solid electrolyte:
s1, preparation of Ba having a double perovskite Structure according to the method of example 31.0Co0.7Fe0.2Nb0.1O3-δPowder;
s2, ba with double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δMixing the powder with a PVA binder, grinding uniformly, and pressing and forming to obtain a blank;
s3, preserving the temperature of the blank at 1200 ℃ for 2h to obtain the composite material.
Test examples
(1) Characterization test
Fe obtained in example 3 and comparative examples 1 to 63O4XRD (X-ray diffraction) tests are carried out on the BCFN composite solid electrolyte sample, and the results are shown in figures 1 and 2.
Fig. 1 is a result of XRD test of the samples of BCFN solid electrolytes prepared in example 3 and comparative examples 1 to 4, and it can be seen that the diffraction peak of the sample of example 3 is more remarkably protruded and the diffraction curve is smoother than those of comparative examples 1 to 4. Wherein the sample of comparative example 4 had more diffraction impurities, indicating Fe3O4The content of (b) is 50wt%, and the crystallinity of the sample is not pure. The XRD pattern curves of the samples of comparative examples 1-3 are relatively similar, and the diffraction peaks are neither significantly prominent nor excessively numerous as compared to example 3. Finally, the highest diffraction peak value of the samples of the five groups is compared in the graph, so that the sample of the example 3 with the highest peak value can be obviously obtained, and the Fe of the example 3 is shown3O4The BCFN composite solid electrolyte sample has the purest crystallinity and better crystal structure.
Fig. 2 and 3 show XRD test results of samples of the BCFN solid electrolytes prepared in comparative example 5 and comparative example 6, respectively. It can be seen that the diffraction peak of the sample of comparative example 6 is very prominent, and the powder sample with few impurities is relatively pure, while the diffraction peak of the sample of comparative example 5 is not prominent all the time, which indicates that the sample of comparative example 6 obtains a purer BCFN solid electrolyte sample with a better crystal structure.
(2) Electrochemical performance test
The conductivity of the electrolyte samples at different temperatures was tested using an electrochemical analyzer from Shanghai Chenghua instruments. The specific method of the test comprises the following steps: before testing, the diameter and thickness of each sample wafer are measured by a vernier caliper, the data thickness d and the cross-sectional area S are recorded, then the material sample wafer plated with the silver electrode is placed into a tube furnace, and silver wires are respectively connected with the two electrodes of the material and the input end of a testing system. Setting a temperature rise and preservation program of the tube furnace, after the material is heated and stabilized for a period of time, pausing and preserving the temperature for 10min from 400 ℃ to 800 ℃ every 50 ℃, and recording the resistance value R of the material. The conductivity calculation formula of the material is calculated as follows:
σ＝d/(S×R)
after the conductivity is calculated, according to an Arrhenius equation:
in the formula: e is ion migration activation energy; k is Boltzman constant; t is the absolute temperature; a is a pre-exponential factor, and the activation energy is calculated.
FIG. 4 and Table 1 are Fe of example 3 and comparative examples 1-43O4-conductivity test results of the BCFN composite solid electrolyte sample and the BCFN solid electrolyte sample of comparative example 6.
Table 1 conductivity test results for electrolyte samples
As can be seen from FIG. 4 and Table 1, the sample conductivity curves for example 3 are higher than the curves for comparative examples 1-4 and comparative example 6, indicating Fe for example 33O4The conductivity of the-BCFN composite solid electrolyte is far higher than that of the electrolyte without Fe3O4The electrical conductivity of the BCFN solid electrolyte of (a). Comparative example 3 and comparative exampleThe conductivity of the sample of example 4 is below the curve of comparative example 6, indicating Fe3O4In the case of a BCFN composite solid electrolyte, fe3O4At too high a content, the conductivity is lower than that without Fe3O4The electrical conductivity of the BCFN solid electrolyte of (a). The sample of comparative example 1 abruptly changes the conductivity curve to a vertical line at more than 1000K, indicating that it cannot withstand high temperature to cause short circuit at more than 1000K, resulting in abrupt conductivity curve. In summary, the doped magnetite ore should not affect the conductivity of the pure system electrolyte material, and the doped magnetite ore should also have a protective effect on the BCFN double perovskite system.
FIG. 5 and Table 2 are Fe of example 3 and comparative examples 1 to 43O4Results of calculation of activation energies of the BCFN composite solid electrolyte sample and the BCFN solid electrolyte sample of comparative example 6.
TABLE 2 activation energy of electrolyte samples
As can be seen from fig. 5 and table 2, the sample of example 3 has the lowest activation energy. Since lower activation energy indicates higher thermal stability of the material, it indicates that the sample of example 3 has much higher thermal stability than that without Fe3O4BCFN solid electrolyte and Fe3O4Fe in an excessive content3O4-BCFN composite solid electrolyte.
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 (5)
1. Fe3O4-BCFN moderate temperature composite solid electrolyte, characterized in that the composition of the electrolyte comprises Ba1.0Co0.7Fe0.2Nb0.1O3-δAnd Fe3O4，Ba1.0Co0.7Fe0.2Nb0.1O3-δHas a double perovskite structure, delta is oxygen deficiency;
wherein, said Fe3O4-a method for preparing a BCFN intermediate temperature composite solid electrolyte, comprising the following steps:
s1, mixing Fe3O4Powder and Ba with double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δUniformly mixing the powder to obtain mixed powder; wherein, fe3O4The content of the mixed powder is 5-15wt%,
s2, mixing the mixed powder with a binder, grinding uniformly, and performing compression molding to obtain a blank;
s3, preserving the temperature of the blank at 1050-1150 ℃ for 1.5-2.5h to obtain the green body;
wherein said Ba having a double perovskite structure1.0Co0.7Fe0.2Nb0.1O3-δThe preparation method of the powder comprises the following steps:
(1) Push Ba1.0Co0.7Fe0.2Nb0.1O3-δRespectively weighing barium salt, cobalt salt, ferric salt and niobium pentoxide according to the stoichiometric ratio, and dissolving the barium salt, the cobalt salt and the ferric salt in water to obtain a solution A;
(2) Dissolving the niobium pentoxide weighed in the step (1) in a nitric acid solution to obtain a solution B;
(3) After the solution A and the solution B are mixed, adding a proper amount of citric acid and glycol, and uniformly stirring to obtain a mixed solution;
(4) Adjusting the pH value of the mixed solution to 4-8, and then stirring and reacting at 70-85 ℃ to obtain wet gel;
(5) Drying the wet gel at 100-140 ℃ for 8-15h, and then preserving heat at 1150-1250 ℃ for 1.5-2.5h to obtain the gel.
2. Fe of claim 13O4-BCFN mesophilic composite solid electrolyte, whichCharacterized by being Fe3O4The content in the mixed powder is 10wt%.
3. Fe of claim 13O4-BCFN moderate temperature composite solid electrolyte, characterized in that in said step (3), the molar quantity of citric acid added is 1.4-1.6 times the total molar quantity of Ba, co, fe, nb.
4. Fe according to claim 1 or 33O4-BCFN mesophilic composite solid electrolyte, characterized in that in said step (3), the molar quantity of ethylene glycol is added in a quantity of 1.15 to 1.3 times the molar quantity of citric acid.
5. Fe according to any one of claims 1 to 33O4-BCFN medium temperature composite solid electrolyte, characterized in that, the barium salt is barium nitrate, cobalt salt is cobalt nitrate, ferric salt is ferric nitrate.
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